WO2021068600A1 - 分子筛复合物与复合材料及其应用 - Google Patents

分子筛复合物与复合材料及其应用 Download PDF

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Publication number
WO2021068600A1
WO2021068600A1 PCT/CN2020/104505 CN2020104505W WO2021068600A1 WO 2021068600 A1 WO2021068600 A1 WO 2021068600A1 CN 2020104505 W CN2020104505 W CN 2020104505W WO 2021068600 A1 WO2021068600 A1 WO 2021068600A1
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Prior art keywords
molecular sieve
pore volume
composite
composite material
rare earth
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PCT/CN2020/104505
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English (en)
French (fr)
Inventor
袁辉志
刘爱华
刘剑利
徐翠翠
刘增让
陶卫东
常文之
吕才山
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China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
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China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
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Application filed by China Petroleum and Chemical Corp, Qilu Petrochemical Co of Sinopec filed Critical China Petroleum and Chemical Corp
Priority to US17/768,137 priority Critical patent/US12233396B2/en
Priority to EP20874727.9A priority patent/EP4032610A4/en
Priority to CN202080070595.1A priority patent/CN114502272B/zh
Publication of WO2021068600A1 publication Critical patent/WO2021068600A1/zh
Anticipated expiration legal-status Critical
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Definitions

  • the present invention relates to the technical field of desulfurization, in particular to molecular sieve composites and composite materials and their applications.
  • SO 2 is the main reason for the formation of acid rain; SO 2 can destroy the physiological functions of plants and slow down the growth of crops and trees; human inhalation of higher concentrations of SO 2 gas will have a strong stimulating effect on the respiratory tract.
  • SO 2 has received extensive attention. It is reported that SO 2 emissions have caused 40% of China's land area to be harmed by acid rain, and the annual loss caused by this is as high as 110 billion yuan. Therefore, controlling pollution and reducing SO 2 emissions are important tasks for the sustainable development of China's economy and society.
  • flue gas desulfurization technologies at home and abroad are mainly divided into two major categories. The first is the wet method, which uses a certain liquid absorbent, emulsion absorbent or absorption solution to treat the exhaust gas, and the second is the dry method. Use powdery or granular adsorbents, absorbents or catalysts to remove sulfur dioxide from flue gas.
  • the most representative and fastest-growing wet desulfurization technology is alkaline washing desulfurization, such as DuPont TM BELCO's LABSORBTM technology.
  • Dry adsorption desulfurization adsorbents mainly include molecular sieves and activated carbon.
  • Molecular sieve is a crystalline substance with uniform pore size and has selective adsorption characteristics. It can simultaneously remove H 2 S and organic sulfur. After removal, the sulfur content can be reduced to less than 15 mg/m 3. It is an excellent sulfide adsorbent.
  • the molecular sieve adsorbent can be regenerated repeatedly under certain conditions and has a long service life. Under the new situation of increasingly stringent environmental protection requirements, the molecular sieve desulfurization process has broad application prospects.
  • CN104689787A discloses an adsorbent for dechlorination of liquefied petroleum gas and an application method thereof, wherein the adsorbent contains a molecular sieve and a metal oxide with the function of adsorbing chlorine, the molecular sieve has a molar ratio of silicon to aluminum atoms of 1-45, and a specific surface area of 300- 650m 2 /g, the weight ratio of molecular sieve to metal oxide with chlorine adsorption function is 45-98:25-50, among which, the metal oxide with chlorine adsorption function is Na, K, Mg, Ca, Al, lanthanide series metals One or more of oxides of, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Ru, Rh, Pd, Ag, Cd, Au and Pt.
  • CN109277075A discloses a coke oven gas purification adsorbent, which is calculated in parts by weight of the adsorbent and contains the following components:
  • the active element is selected from at least one element of group IA, IIA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII group elements in the periodic table;
  • the hydrophobic molecular sieve adsorbent In A the molecular sieve is selected from at least one of X-type molecular sieve, Y-type molecular sieve, A-type molecular sieve, ⁇ -type molecular sieve, SAPO-type molecular sieve, MCM-22, MCM-49, and MCM-56;
  • the hydrophobic molecular sieve is adsorbed
  • molecular sieve is selected from ZSM type molecular sieve, mordenite, ⁇ type molecular sieve, ZSM-5/mordenite, ZSM-5/ ⁇ zeolite, ZSM-5/Y, MCM-22/mordenite, ZSM-5/ At least one of Magadiite, ZSM-5/ ⁇ zeolite/mordenite, ZSM
  • the purpose of the present invention is to overcome the problems in the prior art that it is difficult to balance the desulfurization rate and the penetration sulfur capacity, and to provide a molecular sieve composite and composite material, and a preparation method and application thereof.
  • the content of macropores or mesopores in conventional molecular sieve adsorbents is relatively high, and the effect of adsorption and desulfurization is relatively poor.
  • the inventor of the present invention found that the introduction of aluminum binders controls the content of micropores in molecular sieve adsorbents.
  • Introducing specific metal oxides according to a specific content relationship can significantly improve the desulfurization effect.
  • the precursors of alkaline earth metals can be kneaded and roasted in a specific ratio with the rare earth modified molecular sieve with specific pore distribution in the presence of aluminum precursors.
  • one aspect of the present invention provides a molecular sieve composite, which is characterized in that the molecular sieve composite
  • the compound contains aluminum oxides, alkaline earth metal oxides and rare earth modified molecular sieves, wherein the rare earth modified molecular sieve is a molecular sieve doped with rare earth elements, and the molecular sieve composite pores with a pore size of less than 3 nm account for The percentage of the pore volume to the total pore volume is ⁇ 63.5%; and the molecular sieve composite satisfies the following formula I:
  • W 1 represents the weight content of total aluminum in the molecular sieve composite in terms of aluminum oxide
  • W 2 represents the weight content of alkaline earth metal oxides in the molecular sieve composite
  • W 3 represents the weight content of rare earth elements as oxides in the molecular sieve composite
  • W 4 represents the weight content of the molecular sieve calculated as SiO 2 in the molecular sieve composite.
  • the second aspect of the present invention provides a composite material, which contains the molecular sieve composite as described above and an auxiliary agent loaded on the molecular sieve composite.
  • the third aspect of the present invention provides the application of the above-mentioned molecular sieve composite or composite material in adsorption desulfurization.
  • the fourth aspect of the present invention provides a system with desulfurization function, which includes:
  • Oxidation unit used to treat sulfur-containing gas and recover sulfur
  • the hydrogenation purification unit is connected to the oxidation unit and is used to perform hydrogenation reduction on the oxidation tail gas discharged from the oxidation unit and recover hydrogen sulfide in the reduction product obtained by the hydrogenation reduction;
  • Incineration unit for incineration of the purified tail gas discharged from the hydrogenation purification unit
  • the adsorption unit is used to adsorb SO 2 in the SO 2 -containing flue gas obtained by incineration, and the adsorbent used in the adsorption unit is a composite material as described above.
  • the fifth aspect of the present invention provides a desulfurization method, which includes:
  • the present invention has the following advantages:
  • the composite material of the present invention as an adsorbent has higher saturated sulfur capacity and penetration sulfur capacity.
  • the specific surface area of the composite material is greater than 550m 2 /g and the pore volume is greater than 0.25ml/g, which ensures that the composite material has good adsorption.
  • the saturated sulfur capacity is ⁇ 12%, and the sulfur capacity when the SO 2 removal rate drops to 99% ( The breakthrough sulfur capacity) is greater than 10%, and the total time used to reach the breakthrough sulfur capacity is longer.
  • the composite material adopting the present invention has good regeneration performance and can be recycled for many times.
  • the composite material of the present invention can promote the development of dry desulfurization technology and provide a clean, no secondary pollution, and a sulfur-containing waste gas treatment method that meets environmental protection requirements.
  • Fig. 1 is a schematic structural diagram of a system according to a preferred embodiment of the present invention.
  • Figure 2 is a schematic structural diagram of a system according to another preferred embodiment of the present invention.
  • Fig. 3 is an X-ray diffraction pattern of a composite material according to an embodiment of the present invention.
  • Fig. 4 is an X-ray diffraction pattern of a composite material according to another embodiment of the present invention.
  • the first adsorption tower 42 The second adsorption tower
  • the volume of the gas is expressed in terms of the volume under standard conditions (STP) (0°C (273K), 1.01 ⁇ 10 5 Pa); the "silicon to aluminum ratio” refers to silicon and The molar ratio between aluminum elements; “ppm” is the volume concentration unit; pressure refers to gauge pressure.
  • STP standard conditions
  • ppm is the volume concentration unit
  • pressure refers to gauge pressure.
  • saturated sulfur capacity refers to the maximum amount of sulfur that can be absorbed by the desulfurizer per unit weight, that is, the fresh adsorbent is continuously in contact with the sulfur-containing gas. When the sulfur content of the sulfur-containing gas before and after the contact with the adsorbent is equal, the adsorbent adsorbs The sulfur content accounts for the weight percentage of the adsorbent as the saturated sulfur capacity.
  • Three-through sulfur capacity refers to the amount of sulfur that the adsorbent can absorb when the gas volumetric space velocity is 1750h -1 and the reaction temperature is 120°C while ensuring the process purification index (when the removal rate drops to 99%) Percent by weight.
  • the present invention provides a molecular sieve composite, characterized in that the molecular sieve composite contains aluminum oxide, alkaline earth metal oxide and rare earth modified molecular sieve, wherein the rare earth modified molecular sieve is doped with rare earth elements Molecular sieve, the pore volume of the pores with a pore diameter below 3 nm in the molecular sieve composite accounts for ⁇ 63.5% of the total pore volume; and the molecular sieve composite satisfies the following formula I:
  • W 1 represents the weight content of total aluminum in the molecular sieve composite in terms of aluminum oxide
  • W 2 represents the weight content of alkaline earth metal oxides in the molecular sieve composite
  • W 3 represents the weight content of rare earth elements as oxides in the molecular sieve composite
  • W 4 represents the weight content of the molecular sieve calculated as SiO 2 in the molecular sieve composite.
  • total aluminum refers to the sum of aluminum oxide and the aluminum element provided in the rare earth modified molecular sieve, and its content is calculated as Al 2 O 3 ; the content of alkaline earth metal oxides is calculated as divalent metal oxide; Among the elements, the content of cerium is calculated as CeO 2 and the content of rare earth elements other than cerium is calculated as trivalent metal oxide.
  • the pore volume of the pores with a pore diameter below 3 nm in the molecular sieve composite is preferably 63.5-72% of the total pore volume.
  • the pore volume of the pores with a pore diameter of less than 2 nm in the molecular sieve composite accounts for ⁇ 35% of the total pore volume, and further preferably 39 to 45.5%.
  • the pore volume of pores with a pore diameter of 2-3 nm in the molecular sieve composite accounts for 20-30% of the total pore volume.
  • the pore volume of pores with a pore diameter greater than 3 nm in the molecular sieve composite accounts for 25-40% of the total pore volume.
  • the molecular sieve composite with the pore size distribution in the above-mentioned preferred range can obtain an adsorbent with more excellent desulfurization performance.
  • the weight ratio between the aluminum oxide and the molecular sieve is preferably (8-35): 100, more preferably (12-28): 100, such as 12: 100, 15: 100 , 18:100, 19:100, 20:100, 25:100, 26:100, 27:100, 28:100 or any value between the above values.
  • the weight percentage of the molecular sieve in the molecular sieve composite or composite material can be characterized and calculated according to the relative crystallinity of the molecular sieve composite or composite material.
  • the relative crystallinity is measured by XRD method, the instrument is Rigaku Dmax-2500 X-ray diffractometer, adopts Cuk ⁇ radiation, graphite single crystal filter, operating tube voltage 35KV, tube current 40mA, scanning speed (2 ⁇ ) is 2°/min, and the scanning range is 4°-35°; standard sample is NaY molecular sieve, silicon-to-aluminum ratio is 5, specific surface area is 850m 2 /g, pore volume is 0.32ml/g, pore volume less than 2nm accounts for 32.7%, pores of 2-3nm The volume percentage is 22.8%, and the volume percentage of pores larger than 3 nm is 44.5%.
  • the weight ratio between the alkaline earth metal oxide and the molecular sieve is preferably (0.5-3): 100, more preferably (0.6-2.1): 100, such as 0.6: 100, 1: 100, 1.1:100, 1.2:100, 1.3:100, 1.8:100, 1.9:100, 2:100, 2.1 or any value between the above values.
  • the weight ratio between the rare earth element and the molecular sieve is preferably (2.5-10): 100, more preferably (3.7-9.3): 100, such as 3.7: 100, 4: 100, 5 :100, 5.1:100, 5.4:100, 5.5:100, 6:100, 6.4:100, 6.5:100, 6.9:100, 7.5:100, 7.9:100, 8:100, 9.2:100, 9.3:100 Or any value between the above values.
  • the aluminum oxide may be common aluminum oxides of different valence states, especially common aluminum oxides obtained after high-temperature firing of aluminum precursors.
  • the oxide of aluminum is Al 2 O 3 .
  • the alkaline earth metal oxides can be common alkaline earth metals of different valences (such as beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium ( Ra)) oxides, especially the oxides of common alkaline earth metal precursors calcined at high temperature.
  • the oxide of the alkaline earth metal is at least one of CaO, MgO and BaO.
  • the rare earth elements may be common rare earth elements, such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu) , Gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc) .
  • the rare earth element is Ce and/or La.
  • the rare earth elements are Ce and La, and the weight ratio of Ce to La is 1-3. Selecting preferred rare earth element oxides can further improve the adsorption performance of the composite material prepared based on the molecular sieve composite.
  • the rare earth modified molecular sieve may be a conventional rare earth modified molecular sieve, especially a rare earth modified Y-type molecular sieve, preferably a rare earth modified NaY molecular sieve.
  • the rare earth element is bonded to the pores of the molecular sieve in the form of cations.
  • the specific surface area of the molecular sieve composite is ⁇ 550 m 2 /g, more preferably 550-600 m 2 /g.
  • the pore volume of the molecular sieve complex is ⁇ 0.25ml/g, more preferably 0.25-0.4ml/g.
  • the present invention provides a method for preparing a molecular sieve composite, characterized in that the method comprises: in the presence of a solvent, the precursor of aluminum, the precursor of alkaline earth metal, rare earth modified molecular sieve and optional non-metal
  • the binder is kneaded, formed, dried and roasted, wherein the rare earth modified molecular sieve is a molecular sieve doped with rare earth elements, and the amount of the aluminum precursor, the alkaline earth metal precursor and the rare earth modified molecular sieve is such that
  • the content of aluminum element, alkaline earth metal element, rare earth element and molecular sieve in the molecular sieve composite satisfies formula I, wherein the weight of aluminum element, alkaline earth metal element and rare earth element is calculated as oxide.
  • the amount of the aluminum precursor and the rare earth modified molecular sieve is such that the weight ratio between the aluminum element and the molecular sieve in the resulting molecular sieve composite is preferably (8-35): 100, and more Preferably it is (12-28):100.
  • the amount of the alkaline earth metal precursor and the rare earth modified molecular sieve is such that the weight ratio between the alkaline earth metal element and the molecular sieve in the resulting molecular sieve composite is preferably (0.5-3): 100 , More preferably (0.6-2.1):100.
  • the amount of the rare earth element is such that the weight ratio between the rare earth element and the molecular sieve in the resulting molecular sieve composite is preferably (2.5-10): 100, more preferably (3.7-9.3) :100.
  • the precursor of aluminum is aluminum oxide and/or aluminum hydroxide, more preferably aluminum hydroxide and/or pseudo-thin water. Bauxite.
  • the precursor of the alkaline earth metal is an oxide of alkaline earth metal, hydroxide of alkaline earth metal, carbonate of alkaline earth metal and nitric acid of alkaline earth metal.
  • At least one of the salts is more preferably at least one of calcium oxide, calcium carbonate, calcium nitrate, magnesium oxide, magnesium carbonate, magnesium nitrate, barium nitrate, barium oxide, and barium carbonate.
  • the rare earth elements may be common rare earth elements, such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu) , Gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc) .
  • the rare earth element is Ce and/or La.
  • the rare earth elements are Ce and La, and the weight ratio of Ce to La is 1-3. Selecting preferred rare earth element oxides can further improve the adsorption performance of the final composite material.
  • the rare earth modified molecular sieve may be a conventional rare earth modified molecular sieve, especially a rare earth modified Y-type molecular sieve, preferably a rare earth modified NaY molecular sieve.
  • the rare earth element is bonded to the pores of the molecular sieve in the form of cations.
  • the non-metallic binder is a selective substance, and the use of the non-metallic binder facilitates the formation of the molecular sieve composite.
  • the weight ratio of the molecular sieve to the non-metallic binder is 100:(1-3).
  • the non-metallic binder can be various existing binders that do not contain metal elements.
  • the non-metallic binder is an organic acid and/or an inorganic acid, and more preferably is nitric acid. , At least one of hydrochloric acid, sulfuric acid and citric acid.
  • the rare earth modified molecular sieve can be obtained in a conventional manner.
  • the silicon to aluminum ratio of the molecular sieve is 2-10, more preferably 4.5-7.
  • the specific surface area of the molecular sieve is ⁇ 600 m 2 /g, more preferably 700-1000 m 2 /g.
  • the pore volume of the molecular sieve is ⁇ 0.3ml/g, more preferably 0.3-0.35ml/g.
  • the molecular sieve is NaY molecular sieve.
  • the percentage of the pore volume occupied by pores with a pore diameter of less than 2 nm to the total pore volume is preferably 20-35%, and the percentage of the pore volume occupied by pores with a pore diameter of 2-3 nm to the total pore volume is preferably 10- 26%, the percentage of the pore volume occupied by pores with a pore diameter greater than 3 nm to the total pore volume is preferably 40-65%.
  • the water-soluble rare earth metal salt can be various substances that are dissolved in water to produce rare earth metal ions.
  • the water-soluble rare earth metal salt is a nitrate of a rare earth metal and/or a chloride of a rare earth metal, and more preferably is nitric acid. At least one of cerium, cerium chloride, lanthanum nitrate, and lanthanum chloride.
  • the mixing conditions include: a temperature of 70-90°C.
  • the mixing conditions further include: the time is 20min-3h.
  • the drying conditions may include: a drying temperature of 100-160°C, preferably 110-130°C.
  • the drying conditions may also include: the drying time is 4-6 hours.
  • the calcination conditions may include: the calcination temperature is 400-700°C, preferably 450-600°C.
  • the calcination conditions may also include: the calcination time is 3-8h, preferably 4-6h.
  • the solvent can be a common organic solvent and/or inorganic solvent.
  • the solvent is water.
  • Those skilled in the art can control the amount of solvent according to the requirements of kneading and molding, which will not be repeated here.
  • conventional methods can be used for kneading and molding.
  • molding equipment such as an extruder, can be used.
  • the present invention also provides a molecular sieve composite prepared by the method described above.
  • the present invention provides a composite material, which is characterized in that the composite material contains the molecular sieve composite as described above and an auxiliary agent loaded on the molecular sieve composite.
  • the percentage of the pore volume occupied by pores with a pore diameter of less than 3 nm in the total pore volume in the composite material is preferably ⁇ 65%, more preferably 65-75%.
  • the percentage of the pore volume occupied by pores with a pore diameter of less than 2 nm in the total pore volume in the composite material is ⁇ 45%, and further preferably 45-55%.
  • the pore volume of pores with a pore diameter of 2-3 nm in the composite material accounts for 15-35% of the total pore volume.
  • the pore volume of pores with a pore diameter greater than 3 nm in the composite material accounts for 20-35% of the total pore volume.
  • the composite material with the pore size distribution within the above-mentioned preferred range has more excellent desulfurization performance.
  • the composite material has an X-ray diffraction pattern substantially as shown in FIG. 3.
  • the composite material has an X-ray diffraction pattern as shown in Table 1-a below:
  • the XRD spectrum of the composite material is similar to that of the unmodified molecular sieve, and no characteristic diffraction peaks of other oxides are found.
  • the introduction of rare earth metals did not destroy the framework structure of the molecular sieve, and the rare earth metals were uniformly dispersed on the molecular sieve.
  • the characteristic diffraction peaks of modified molecular sieves such as rare earth metals are significantly reduced, which is caused by the higher absorption coefficient of rare earth metal oxides.
  • the weight ratio between the auxiliary agent and the molecular sieve is preferably (0.8-4): 100, more preferably (1.2-3.3): 100, such as 1.2: 100, 1.5: 100, 1.8: 100, 2: 100 , 2.5:100, 2.6:100, 2.7:100, 2.8:100, 3:100, 3.3:100 or any value between the above values.
  • the auxiliary agent may be an existing metal oxide with auxiliary desulfurization function, such as an oxide of a group VIB or group VIII metal.
  • the auxiliary agent is preferably an oxide of nickel or an oxide of cobalt. And at least one of molybdenum oxide.
  • the nickel oxide may be common nickel oxides with different valence states, especially common nickel precursors that are calcined at a high temperature.
  • the oxide of nickel is NiO.
  • the cobalt oxide may be a common cobalt oxide with different valences, especially an oxide obtained after a common cobalt precursor is calcined at a high temperature.
  • the oxide of cobalt is CoO.
  • the molybdenum oxide can be common molybdenum oxides with different valence states, especially common molybdenum precursors that are calcined at a high temperature.
  • the oxide of molybdenum is MoO 3 .
  • the specific surface area of the composite material is ⁇ 550 m 2 /g, more preferably 558-580 m 2 /g.
  • the pore volume of the composite material is ⁇ 0.25ml/g, more preferably 0.26-0.3ml/g.
  • the saturated sulfur capacity of the composite material is ⁇ 12%, more preferably 12-15%.
  • the penetration sulfur capacity of the composite material is ⁇ 10%, more preferably 10-11%.
  • the molecular sieve composite or composite material of the present invention does not contain detectable amounts of Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, W, Ru, Rh, Pd, Ag, Cd , Au, Y or Pt. More preferably, the molecular sieve composite or composite material of the present invention consists only of the above-mentioned components.
  • the present invention provides a method for preparing a composite material, characterized in that the method includes:
  • the precursor of aluminum, the precursor of alkaline earth metals, the rare earth modified molecular sieve and optional non-metallic binder are kneaded, formed, dried and calcined to obtain a molecular sieve composite, wherein
  • the rare earth modified molecular sieve is a molecular sieve doped with rare earth elements, and the amount of the aluminum precursor, the alkaline earth metal precursor and the rare earth modified molecular sieve is such that the aluminum element, the alkaline earth metal element, and the rare earth element in the resulting molecular sieve composite
  • the relationship between and the amount of molecular sieve satisfies Formula I;
  • the precursor of the auxiliary agent is a precursor of nickel, a precursor of cobalt and a precursor of molybdenum
  • the amount of the precursor of the auxiliary agent is such that the weight ratio of the auxiliary agent to the molecular sieve in the obtained composite material is (0.8-4): 100;
  • the weight of aluminum element, alkaline earth metal element, rare earth element and auxiliary agent is calculated as oxide.
  • the amount of the aluminum precursor and the rare earth modified molecular sieve is such that the weight ratio between the aluminum element and the molecular sieve in the resulting molecular sieve composite is preferably (8-35): 100, more preferably (12- 28):100, such as 12:100, 15:100, 18:100, 19:100, 20:100, 25:100, 26:100, 27:100, 28:100 or any value between the above values.
  • the amount of the alkaline earth metal precursor and the rare earth modified molecular sieve is such that the weight ratio between the alkaline earth metal element and the molecular sieve in the resulting molecular sieve composite is preferably (0.5-3): 100, more preferably ( 0.6-2.1):100, such as 0.6:100, 1:100, 1.1:100, 1.2:100, 1.3:100, 1.8:100, 1.9:100, 2:100, 2.1 or any value between the above values.
  • the amount of the rare earth element is such that the weight ratio between the rare earth element and the molecular sieve in the resulting molecular sieve composite is preferably (2.5-10): 100, more preferably (3.7-9.3): 100, such as 3.7 :100, 4:100, 5:100, 5.1:100, 5.4:100, 5.5:100, 6:100, 6.4:100, 6.5:100, 6.9:100, 7.5:100, 7.9:100, 8:100 , 9.2:100, 9.3:100 or any value between the above values.
  • the amount of the precursor of the auxiliary agent is such that the weight ratio between the auxiliary agent and the molecular sieve in the obtained composite material is preferably (1.2-3.3): 100, such as 1.2: 100, 1.5: 100, 1.8: 100, 2:100, 2.5:100, 2.6:100, 2.7:100, 2.8:100, 3:100, 3.3:100 or any value between the above values.
  • the precursor of aluminum is aluminum oxide and/or aluminum hydroxide, more preferably aluminum hydroxide and/or pseudo-thin water. Bauxite.
  • the precursor of the alkaline earth metal is an oxide of alkaline earth metal, hydroxide of alkaline earth metal, carbonate of alkaline earth metal and nitric acid of alkaline earth metal.
  • At least one of the salts is more preferably at least one of calcium oxide, calcium carbonate, calcium nitrate, magnesium oxide, magnesium carbonate, magnesium nitrate, barium nitrate, barium oxide, and barium carbonate.
  • the rare earth elements may be common rare earth elements, such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu) , Gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc) .
  • the rare earth element is Ce and/or La.
  • the rare earth elements are Ce and La, and the weight ratio of Ce to La is 1-3. Selecting preferred rare earth element oxides can further improve the adsorption performance of the final composite material.
  • the rare earth modified molecular sieve may be a conventional rare earth modified molecular sieve, especially a rare earth modified Y-type molecular sieve, preferably a rare earth modified NaY molecular sieve.
  • the rare earth element is bonded to the pores of the molecular sieve in the form of cations.
  • the non-metallic binder is a selective substance, and the use of the non-metallic binder facilitates the formation of the molecular sieve composite.
  • the weight ratio of the molecular sieve to the non-metallic binder is 100:(1-3).
  • the non-metallic binder can be various existing binders that do not contain metal elements.
  • the non-metallic binder is an organic acid and/or an inorganic acid, and more preferably is nitric acid. , At least one of hydrochloric acid, sulfuric acid and citric acid.
  • the rare earth modified molecular sieve can be obtained in a conventional manner.
  • the silicon to aluminum ratio of the molecular sieve is 2-10, more preferably 4.5-7.
  • the specific surface area of the molecular sieve is ⁇ 600 m 2 /g, more preferably 700-1000 m 2 /g.
  • the pore volume of the molecular sieve is ⁇ 0.3ml/g, more preferably 0.3-0.35ml/g.
  • the molecular sieve is NaY molecular sieve.
  • the percentage of the pore volume occupied by pores with a pore diameter of less than 2 nm to the total pore volume is preferably 20-35%, and the percentage of the pore volume occupied by pores with a pore diameter of 2-3 nm to the total pore volume is preferably 10- 26%, the percentage of the pore volume occupied by pores with a pore diameter greater than 3 nm to the total pore volume is preferably 40-65%.
  • the water-soluble rare earth metal salt can be various substances that are dissolved in water to produce rare earth metal ions.
  • the water-soluble rare earth metal salt is a nitrate of a rare earth metal and/or a chloride of a rare earth metal, and more preferably is nitric acid. At least one of cerium, cerium chloride, lanthanum nitrate, and lanthanum chloride.
  • the mixing conditions include: a temperature of 70-90°C.
  • the mixing conditions further include: the time is 20min-3h.
  • the drying conditions may include: a drying temperature of 100-160°C, preferably 110-130°C.
  • the drying conditions may also include: the drying time is 4-6 hours.
  • the firing conditions may include: the firing temperature is 400-700°C, preferably 450-600°C.
  • the calcination conditions may also include: the calcination time is 3-8h, preferably 4-6h.
  • the precursor of the additive is at least one of soluble nickel salt, soluble cobalt salt and soluble molybdenum salt, preferably nickel nitrate, cobalt nitrate, molybdenum nitrate, nickel chloride, cobalt chloride and chloride At least one of molybdenum, nickel sulfate, cobalt sulfate, and molybdenum sulfate.
  • the drying conditions may include: the drying temperature is 100-160°C, preferably 110-130°C.
  • the drying conditions may also include: the drying time is 4-6 hours.
  • the firing conditions may include: the firing temperature is 400-700°C, preferably 450-600°C.
  • the calcination conditions may also include: the calcination time is 3-8h, preferably 4-6h.
  • a conventional method can be used to load the molecular sieve composite with the auxiliary agent.
  • the method for loading the molecular sieve composite with the auxiliary agent is: The molecular sieve composite is impregnated with equal volume, the impregnated material is dried, and the dried product is roasted.
  • the conditions of equal volume impregnation include: the temperature is 5-40°C, and more preferably 20-30°C. More preferably, the conditions of the equal volume immersion further include: the time is 20 min-2.5 h, more preferably 0.5-1 h.
  • the conditions for drying the impregnated substance include: a temperature of 80-160°C, more preferably 110-130°C. More preferably, the conditions for drying the impregnated substance further include: the time is 2-10 hours, and more preferably 4-6 hours.
  • the conditions for calcining the dried product include: the calcining temperature is 300-500°C, more preferably 350-450°C. More preferably, the conditions for roasting the dried product further include: the roasting time is 2-10 hours, more preferably 3-5 hours.
  • the solvent there is no special requirement on the solvent, and it can be a common organic solvent and/or inorganic solvent. But preferably, the solvent is water. Those skilled in the art can control the amount of solvent according to the requirements of kneading and molding, which will not be repeated here.
  • conventional methods can be used for kneading and molding.
  • molding equipment such as an extruder, can be used.
  • the present invention also provides a composite material prepared by the method described above.
  • the present invention also provides the application of modified activated carbon or composite materials as described above in adsorption desulfurization, especially in samples with low sulfur content (such as sulfur dioxide content not higher than 0.2% by volume (ie 6000 mg/m 3 ) Gas samples, such as flue gas) for adsorption desulfurization applications.
  • the present invention also provides a desulfurization method, characterized in that the method includes: contacting the sulfur-containing gas to be processed with the composite material as described above;
  • the method includes: preparing the composite material according to the method described above; and then contacting the sulfur-containing gas with the obtained composite material.
  • the desulfurization method according to the present invention is particularly suitable for the removal of sulfur in samples with low sulfur content. Therefore, preferably, the sulfur dioxide content in the sulfur-containing gas is not higher than 0.2% by volume. On the other hand, when the content of sulfur dioxide in the sulfur-containing gas is higher than 0.2% by volume, the method preferably further includes reducing the content of sulfur dioxide in the sulfur-containing gas to 0.2% by volume or less before contacting with the composite material.
  • the contact conditions include: a temperature of 100-150°C.
  • the contact conditions further include: the gas volumetric space velocity is 1500-2000 h -1 .
  • the method further includes: regenerating the composite material.
  • the regeneration method may be thermal regeneration and/or water washing regeneration.
  • the composite material of the present invention can be thermally regenerated and/or washed and regenerated under conventional conditions.
  • the thermal regeneration method is gas purging
  • the gas purging conditions include: the gas volumetric space velocity is 1000-1500h -1 , the temperature is 150-250°C, and the purged gas is an inert gas (such as Nitrogen).
  • the conditions for the water washing regeneration include: a liquid hourly space velocity of 0.5-1.5 h -1 , and a temperature of 25-40°C.
  • the sulfur-containing gas is at least one of the flue gas of the heating furnace of the petroleum refining industry, the sulfur tail gas and the catalytic cracking regeneration flue gas.
  • the present invention also provides a system with desulfurization function, which is characterized in that the system includes:
  • Oxidation unit used to treat sulfur-containing gas and recover sulfur
  • the hydrogenation purification unit is connected to the oxidation unit and is used to perform hydrogenation reduction on the oxidation tail gas discharged from the oxidation unit and recover hydrogen sulfide in the reduction product obtained by the hydrogenation reduction;
  • Incineration unit for incineration of the purified tail gas discharged from the hydrogenation purification unit
  • the adsorption unit is used to adsorb SO 2 in the SO 2 -containing flue gas obtained by incineration, and the adsorbent used in the adsorption unit is a composite material as described above.
  • the adsorption unit in order to facilitate the regeneration of the composite material in the adsorption unit, includes an inlet and an outlet for regenerating organisms, thereby facilitating the introduction of regenerates (heat source or washing water) into the adsorption unit to regenerate the composite material.
  • the adsorption unit is preferably further connected to the oxidation unit, so that the regenerated SO 2 containing regeneration gas is returned to the oxidation unit for reprocessing.
  • the adsorption unit includes at least two adsorption towers (such as the first adsorption tower 41 and the second adsorption tower 42), which are used alternately for continuous adsorption and incineration.
  • the SO 2 in the flue gas containing SO 2 in the flue gas containing SO 2 .
  • hot gas such as hot nitrogen
  • the generated regeneration gas can be discharged from the top of the adsorption tower, and can be further introduced into the oxidation unit to perform Process again.
  • washing water can be introduced from the top of the adsorption tower, and the regenerated dilute acid generated is discharged from the bottom of the adsorption tower, and can be further introduced into the oxidation unit for reprocessing.
  • the oxidation unit may include a liquid sulfur pool 17 and a thermal reaction furnace 11, a first-stage condenser 12, and a catalytic converter connected in sequence.
  • the liquid sulfur pool 17 is connected with the first-stage condenser 12 and a catalytic converter.
  • the device is connected to collect the cooled liquid sulfur.
  • the oxidation unit includes a liquid sulfur pool 17 and a thermal reaction furnace 11, a primary condenser 12, a primary catalytic converter 13, a secondary condenser 14, and a secondary catalytic converter connected in sequence.
  • the converter 15 and the three-stage condenser 16 are connected to the first-stage condenser 12, the second-stage condenser 14 and the third-stage condenser 16 respectively, and the liquid sulfur pool 17 is used to collect the cooled liquid sulfur.
  • the hydrogenation purification unit may include a hydrogenation reactor 21, a hydrogenation tail gas cooler 22, a quench tower 23, and an absorption tower 24 connected in sequence.
  • the oxidation tail gas discharged from the oxidation unit undergoes hydrogenation reduction in the hydrogenation reactor 21, and then enters the hydrogenation tail gas cooler 22 and the quench tower 23 to be cooled, and then enters the absorption tower 24 to absorb hydrogen sulfide in the reduction product.
  • the incineration unit may be an incinerator and/or a catalytic incineration reactor.
  • the oxidation unit, the hydrogenation purification unit and the incineration unit are used to reduce the content of sulfur (mainly including hydrogen sulfide) in the sulfur-containing gas, and the adsorption unit provided with an adsorption material is used to further reduce the content of sulfur dioxide .
  • the present invention also provides a desulfurization method, characterized in that the method includes:
  • the contact conditions include: a temperature of 100-150°C.
  • the contact conditions further include: the gas volumetric space velocity is 1500-2000 h -1 .
  • the method also includes regenerating the adsorbent.
  • the regeneration method may be thermal regeneration and/or water washing regeneration.
  • the composite material of the present invention can be thermally regenerated and/or washed and regenerated under conventional conditions.
  • the method further includes regenerating the adsorbent, and returning the regenerated SO 2 -containing regeneration gas to step (a) for reprocessing.
  • the thermal regeneration method is gas purging
  • the gas purging conditions include: the gas volumetric space velocity is 1000-1500h -1 , the temperature is 150-250°C, and the purged gas is an inert gas (such as Nitrogen).
  • the conditions for the water washing regeneration include: a liquid hourly space velocity of 0.5-1.5 h -1 , and a temperature of 25-40°C.
  • step (a) there is no special requirement for the oxidation in step (a), as long as it can cause the sulfur-containing gas to undergo Claus reaction to obtain sulfur.
  • the way of oxidation may be: burning sulfur-containing gas, one-stage cooling, and catalytic reaction in sequence.
  • the combustion conditions include: a temperature of 900-1400°C and a residence time of 2-3s.
  • "residence time” refers to the residence time of the sulfur-containing gas in the combustion vessel, that is, the time from entering the furnace to exiting the furnace, that is, the reaction time of the gas.
  • condition of the primary cooling is such that the temperature of the cooled gas is 120-180°C.
  • the conditions for the catalytic reaction include: the catalyst is an alumina-based catalyst and/or a titania-based catalyst, the gas volumetric space velocity is 500-1000 h -1 , and the temperature is 200-350°C.
  • the method of the catalytic reaction is to sequentially perform a first-stage catalytic reaction, a second-stage cooling, a second-stage catalytic reaction, and a third-stage cooling.
  • the conditions of the first-stage catalytic reaction include: the catalyst is an alumina-based catalyst and/or a titania-based catalyst, the gas volumetric space velocity is 600-800 h -1 , and the temperature is 290-330°C.
  • the conditions of the secondary cooling are such that the temperature of the cooled gas is 130-160°C.
  • the conditions of the secondary catalytic reaction include that the catalyst is an alumina-based catalyst, the gas volumetric space velocity is 600-800 h -1 , and the temperature is 220-250°C. Further preferably, the condition of the three-stage cooling is such that the temperature of the cooled gas is 130-160°C.
  • the main component of the alumina-based catalyst is Al 2 O 3 , the specific surface area is greater than or equal to 350 m 2 /g, and the pore volume is greater than or equal to 0.45 ml/g, which can be obtained commercially, for example, from Shandong Qilu Keli Chemical Research Institute Ltd.'s LS-02 catalyst.
  • the main component of the titanium oxide-based catalyst is TiO 2 , the specific surface area is greater than or equal to 180m 2 /g, and the pore volume is greater than or equal to 0.3ml/g, which can be obtained commercially, for example, LS-981 from Shandong Qilu Keli Chemical Research Institute Co., Ltd. catalyst.
  • the hydrogenation reduction conditions may include: the hydrogenation catalyst is a Co-Mo tail gas hydrogenation catalyst, the gas volumetric space velocity is 500-1000h -1 , and the temperature is 220-350°C .
  • the method for recovering the hydrogen sulfide in the reduction product obtained by the hydrogenation reduction is: cooling the reduction product obtained by the hydrogenation reduction to 30-40° C., and using an amine solution to absorb the hydrogen sulfide in the product after the temperature reduction.
  • the concentration of the amine in the amine solution can be 20-50% by weight.
  • the amine in the amine solution can be various alcohol amine desulfurizers, of which methyldiethanolamine (MDEA) is preferred.
  • MDEA methyldiethanolamine
  • the amine solution can be KMKTS-15 high-efficiency desulfurizing agent from Zibo Kaimeike Industry and Trade Co., Ltd.
  • the Co-Mo-based tail gas hydrogenation catalyst may be a Claus tail gas low-temperature hydrogenation catalyst with modified Al 2 O 3 as a carrier and cobalt, molybdenum, etc. as active metal components, with a specific surface area ⁇ 200m 2 / g, can be obtained commercially, for example, LSH-02 catalyst purchased from Shandong Qilu Keli Chemical Research Institute Co., Ltd.
  • the Co-Mo tail gas hydrogenation catalyst can also be a special catalyst for Claus tail gas hydrogenation using modified Al 2 O 3 as the carrier and cobalt and molybdenum as the active metal components.
  • the specific surface area is ⁇ 300m 2 /g.
  • LS-951T catalyst purchased from Shandong Qilu Keli Chemical Research Institute Co., Ltd.
  • the incineration conditions may include a temperature of 600-800°C and a residence time of 2-3s.
  • the incineration in step (c), can be a conventional incineration method.
  • the method of incineration is catalytic incineration
  • the conditions of the catalytic incineration include: the catalyst is a catalytic incineration catalyst containing iron and vanadium, the temperature is 250-350°C, and the space velocity is 500-1000 h -1 .
  • the specific composition of the catalytic incineration catalyst containing iron and vanadium is: Fe 2 O 3 2-8% by weight, V 2 O 5 is 1-4% by weight, and the balance is white carbon black.
  • the content of CO 2 in the sulfur-containing gas is 3-5%
  • the volume content of SO 2 is 20-1000 ppm
  • the volume content of NOx is 20-150 ppm
  • the content of O 2 is 3-5%
  • H The content of 2 O is 3-10% by weight.
  • the method is implemented in the system as described above.
  • the original molecular sieve powder was purchased from Qilu Branch of Sinopec Catalyst Co., Ltd.;
  • Alkaline silica sol was purchased from Qingdao Zhongneng Silicon Chemical Co., Ltd.;
  • Aluminum hydroxide dry glue was purchased from Yangzhou Dilan Chemical Materials Co., Ltd.;
  • the pseudo-boehmite was purchased from Shandong Dezhou Jinghuo Technology Glass Co., Ltd.;
  • the model of the extruder is ZYDJ-30, and the manufacturer is Zibo Yuecheng Machinery Co., Ltd.;
  • the determination method of element composition is X-ray fluorescence method, and the specific detection refers to GB/T 30905-2014, and combined with X-ray photoelectron spectroscopy to determine the valence state of the element; the molecular sieve and Al 2 O 3 in Table 2 and Table 3 are based on the dosage show;
  • the rare earth chloride solution into the beaker and stir evenly, adjust the pH to about 4 with hydrochloric acid, place the beaker in a water bath and heat to about 80°C, exchange for 1 hour while stirring, and the exchange process ends. Cooling, filtering, washing and drying.
  • the molecular sieve after the first exchange was calcined and calcined at 550°C for 4 hours. After roasting, the molecular sieve is exchanged twice according to the above method to obtain a modified molecular sieve.
  • the adsorbent was prepared according to the steps and conditions of Example 1, except that the composition, preparation conditions or concentration of the immersion solution were changed.
  • the specific preparation conditions are shown in Table 1.
  • the content of each metal oxide and molecular sieve in the final adsorbent product (weight percentage ) As shown in Table 2, the measurement results of specific surface area are shown in Table 4.
  • the XRD spectra data of the obtained adsorbent are shown in Table 2-2 to Table 2-7, and the XRD spectra are similar to those in Figure 3.
  • the adsorbent was prepared according to the steps and conditions of Example 1, except that nickel nitrate was replaced with cobalt nitrate of equal weight (calculated as metal oxide).
  • the measurement results of specific surface area are shown in Table 4.
  • the XRD spectrum data of the obtained adsorbent is shown in Table 2-8.
  • the adsorbent was prepared according to the steps and conditions of Example 1, except that nickel nitrate was replaced with molybdenum nitrate of equal weight (calculated as metal oxide).
  • the measurement results of specific surface area are shown in Table 4.
  • the XRD spectrum data of the obtained adsorbent is shown in Table 2-9.
  • the adsorbent was prepared according to the steps and conditions of Example 2, except that the NaY molecular sieve was replaced with 13X molecular sieve (purchased from Tianjin Damao Chemical Reagent Factory, the specific surface area is 724m 2 /g, the pore volume is 0.34ml/g, less than 2nm The pore volume ratio of the pore volume is 28.5%, the pore volume ratio of 2-3 nm is 26%, and the pore volume ratio of pores larger than 3 nm is 45.5%). The measurement results of the specific surface area are shown in Table 4.
  • the adsorbent was prepared according to the steps and conditions of Example 1, except that the concentration of the immersion solution was changed, so that the content of each metal oxide and molecular sieve (unit: wt%) in the final adsorbent product is shown in Table 3. See Table 4 for the measurement results of surface area.
  • the adsorbent was prepared according to the steps and conditions of Example 1, except that nickel nitrate was replaced with iron nitrate and zinc nitrate of equal weight (calculated as metal oxide). The measurement results of specific surface area are shown in Table 4.
  • the adsorbent was prepared according to the steps and conditions of Example 1, except that lanthanum chloride and cerium chloride were replaced with equal weight of nickel nitrate.
  • the measurement results of specific surface area are shown in Table 4.
  • the adsorbent was prepared according to the steps and conditions of Example 1, except that the calcium oxide was replaced with sodium oxide of equal weight (calculated as metal oxide). The measurement results of the specific surface area are shown in Table 4.
  • the adsorbent was prepared according to the steps and conditions of Example 1, except that the aluminum hydroxide dry glue was replaced with an alkaline silica sol of equal weight.
  • the measurement results of the specific surface area are shown in Table 4.
  • the adsorbent was prepared according to the steps and conditions of Example 1. The difference was that instead of preparing the rare earth modified molecular sieve in advance, cerium chloride and lanthanum chloride and nickel nitrate were used to form a co-immersion solution and an isometric impregnating adsorbent carrier. Proceed as follows:
  • the reactor of the micro reaction device is made of a stainless steel tube with an inner diameter of 20 mm, and the reactor is placed in a thermostat.
  • the adsorbent is filled with 10ml, and the upper part is filled with quartz sand of the same particle size for mixing and preheating.
  • the sulfur chromatograph produced by AC Company was used to analyze the content of SO 2 in the inlet and outlet gas of the reactor.
  • the chromatographic operating conditions are as follows:
  • Chromatographic column stainless steel column length 30m, inner diameter 0.32mm, liquid film thickness 4 ⁇ m; liquid film specification PDMS-1
  • the inlet gas volume composition is CO 2 3 vol%, SO 2 0.03 vol% (900 mg/m 3 ), H 2 O 3 vol%, the rest is N 2 , the gas volumetric space velocity is 1750 h -1 , and the reaction temperature is 120°C.
  • N 0 and N 1 represent the volume concentration of SO 2 at the inlet and outlet respectively.
  • M sulfur represents the weight of the adsorbent adsorbing sulfur
  • M catalyst represents the weight of the adsorbent used to adsorb sulfur
  • the saturated sulfur capacity refers to the maximum amount of sulfur that the desulfurizer can absorb per unit weight, that is, the fresh adsorbent is continuously mixed with the sulfur-containing gas Contact, when the sulfur content of the sulfur-containing gas before and after contact with the adsorbent is equal, the percentage of the sulfur content adsorbed by the adsorbent to the adsorbent is the saturated sulfur capacity.
  • Penetration sulfur capacity Under certain conditions of use, the weight percentage of sulfur that the adsorbent can absorb while ensuring the process purification index. In other words, when the sulfur content in the export process gas is greater than the process purification index, immediately remove all the spent catalyst, and the sulfur capacity measured by the average sample is called the breakthrough sulfur capacity. In the present invention, when the SO 2 removal rate is reduced to 99%, it is considered that the breakthrough is achieved. That is, the breakthrough sulfur capacity in the present invention refers to the sulfur capacity of the adsorbent when the SO 2 removal rate is reduced to 99%. The total time used by the adsorbent in sulfur capacity is defined as the adsorption time.
  • the adsorbents prepared in Example 1 and Reference Examples 1, 4, and 5 were subjected to a SO 2 removal test (the specific method is the same as that of Test Example 1). When the adsorbent penetrates the SO 2 adsorption, the penetration of the adsorbent is reached. At the time of sulfur permeability, stop the adsorption of the gas containing SO 2 and switch to nitrogen to investigate the regeneration performance of the adsorbent.
  • the regeneration conditions are: the space velocity is 1200h -1 , the temperature is 200 °C, the purge gas is nitrogen, and the regeneration time is 6 hours.
  • the regenerated adsorbent was used for the SO 2 removal test. When the breakthrough sulfur capacity was reached, it was regenerated. The adsorbent was regenerated 5 times in succession. The results of the adsorbent SO 2 breakthrough sulfur capacity after each regeneration are shown in Table 6. .
  • the system includes:
  • the oxidation unit is used to process sulfur-containing gas and recover sulfur, including a liquid sulfur pool 17 and a thermal reaction furnace 11, a primary condenser 12, a primary catalytic converter 13, a secondary condenser 14, and a secondary catalytic converter connected in sequence
  • the liquid sulfur pool 17 is connected to the first-stage condenser 12, the second-stage condenser 14 and the third-stage condenser 16 respectively, and is used to collect the cooled liquid sulfur;
  • the hydrogenation purification unit is connected to the oxidation unit and is used to hydrogenate and reduce the oxidation tail gas discharged from the oxidation unit and recover the hydrogen sulfide in the reduction product obtained by the hydrogenation reduction.
  • the incineration unit 31 is used for incineration of the purified tail gas discharged from the hydrogenation purification unit;
  • the adsorption unit is used to adsorb SO 2 in the SO 2 -containing flue gas obtained by incineration.
  • the adsorbent used in the adsorption unit is a composite material prepared by the present invention, including a first adsorption tower 41 and a second adsorption tower 42, two Two adsorption towers can be used alternately to achieve continuous adsorption;
  • the heat exchange unit includes a tail gas reheater 111 and a flue gas heat exchanger 222, the tail gas reheater 111 is arranged between the oxidation unit and the hydrogenation purification unit, and is used to heat the oxidation tail gas discharged from the oxidation unit;
  • the gas heat exchanger 222 is arranged between the incineration unit and the adsorption unit, and is used to reduce the temperature of the flue gas generated by the incineration.
  • the thermal reaction unit is acid gas containing 85% by volume of hydrogen sulfide (the content of CO 2 is 10% by volume, the content of hydrocarbons is 2% by volume, and the content of NH 3 is 3% by volume) which is partially burned in the thermal reaction furnace 11 and converted into Sulfur dioxide:
  • the Claus reaction between hydrogen sulfide and sulfur dioxide generates elemental sulfur and process gas.
  • the elemental sulfur After being cooled by the primary condenser 12, the elemental sulfur enters the liquid sulfur pool 17 to obtain liquid sulfur;
  • the process gas sequentially enters the primary catalytic converter 13, the secondary condenser 14, the secondary catalytic converter 15, and the tertiary condenser 16 of the catalytic reaction unit.
  • elemental sulfur enters the liquid sulfur pool 17 through the secondary condenser 14 and the tertiary condenser 16; the reacted Claus tail gas enters the tail gas purification unit.
  • Claus tail gas is heated to 236°C by the tail gas reheater 111 and then enters the hydrogenation reactor 21.
  • the sulfur-containing compounds are hydrogenated to hydrogen sulfide, and then cooled by the hydrogenation tail gas.
  • the reactor 22 and the quench tower 23 cool down and enter the absorption tower 24 with amine liquid (KMKTS-15 high-efficiency desulfurizing agent, purchased from Zibo Kaimeike Industry and Trade Co., Ltd.) to absorb hydrogen sulfide in the hydrogenation tail gas to obtain purified tail gas.
  • amine liquid KMKTS-15 high-efficiency desulfurizing agent, purchased from Zibo Kaimeike Industry and Trade Co., Ltd.
  • the purified tail gas is introduced into the incineration unit (incinerator) 31 for incineration, and flue gas containing SO 2 is generated, and the flue gas is introduced into the adsorption unit.
  • the flue gas is exchanged to 145°C by the flue gas heat exchanger 222 and then enters the first adsorption tower 41 in the adsorption state. After the SO 2 is adsorbed therein, the purified flue gas is discharged through the chimney, and the SO 2 emission control index in the purified flue gas is 20mg/m 3 . At the beginning of operation, no SO 2 was detected in the purified flue gas. After 650h of operation, SO 2 appeared in the flue gas and the concentration was 1mg/m 3.
  • the SO 2 in the flue gas reached 8mg/m 3 , continue to operate After 900 hours, the SO 2 in the flue gas reaches 20 mg/m 3 , the first adsorption tower 41 is removed, and the second adsorption tower 42 is switched to adsorb the incineration tail gas. At the same time, the first adsorption tower 41 is fed with regeneration hot nitrogen for thermal regeneration, and regeneration produces a regeneration gas containing SO 2. The regeneration gas is introduced into the first-stage catalytic converter 13 for reprocessing. The regeneration time is 100h (relative to 20m 3 of adsorbent).
  • the regenerated first adsorption tower 41 is switched to perform adsorption.
  • the SO 2 emission concentration of the flue gas of the sulfur recovery device can be lower than 20mg/m 3 , which meets the requirement of the most stringent environmental protection regulations for flue gas SO 2 to drop below 50mg/m 3 .
  • the regeneration method is simple, and the entire treatment process is continuously cleaned.
  • the acid gas is desulfurized according to the system and method of Test Example 3.
  • the incinerator of the incineration unit is replaced with a catalytic incineration reactor, and the regeneration method is water washing regeneration.
  • the water washing regeneration method is: The washing water is passed into the first adsorption tower 41 to regenerate the adsorbent, and the regenerated dilute acid is generated by regeneration. The regenerated dilute acid is introduced into the thermal reaction furnace 11 for reprocessing. The regeneration time is 140h.
  • the acid gas is desulfurized according to the system and method of Test Example 3. The difference is that the temperature of the adsorption unit is 180° C., and the gas volumetric space velocity is 1000 h -1 . When the running time is 700h, the SO 2 in the flue gas reaches 20mg/m 3 .

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Abstract

一种分子筛复合物、复合材料及应用，分子筛复合物含有铝的氧化物、碱土金属的氧化物和稀土改性分子筛，稀土改性分子筛为掺杂有稀土元素的分子筛，分子筛复合物中孔径在3nm以下的孔所占的孔体积占总孔体积的百分比≥63.5％；且稀土元素的含量与铝的氧化物、碱土金属的氧化物和分子筛的含量之间满足一定的关系式。复合材料含有分子筛复合物和负载于分子筛复合物上的助剂，复合材料可以应用于烟气吸附脱硫。

Description

分子筛复合物与复合材料及其应用 技术领域
本发明涉及脱硫技术领域，具体涉及分子筛复合物与复合材料及其应用。
背景技术
SO 2是形成酸雨的最主要原因；SO 2可破坏植物的生理机能，减缓农作物及树木生长；人体吸入较高浓度SO 2气体，会对呼吸道产生强烈的刺激作用。SO 2作为主要的大气污染物受到人们的广泛重视。据报道SO 2排放造成了我国40％的国土面积受到酸雨危害，每年因此造成的损失高达1100亿元。因此，控制污染、减少SO 2排放，是我国经济社会可持续发展的重要任务。
工业加热炉烟气、硫磺尾气和催化裂化再生烟气中都会产生含SO 2废气，随着环保法规的日益严格，SO 2减排任务迫在眉睫。目前，国内外烟气脱硫技术主要分为两个大的类别，第一种是湿法，即采用某种液体吸收剂、乳液吸收剂或者吸收溶液对废气进行处理，第二种是干法，采用粉状或粒状的吸附剂、吸收剂或催化剂来脱除烟道气中的二氧化硫。湿法脱硫技术中最具代表性、发展最快的是碱洗法脱硫，例如DuPont TM BELCO公司的LABSORBTM技术。采用烟气后碱洗的湿法脱硫技术可以实现50mg/m 3以下的更低排放量，但是该类工艺产生新的二次污染物——含硫酸钠废水，该类废水无法直接排放，再处理工艺投资巨大。目前中石化已全面禁止各类装置新增烟气碱法脱硫工艺。干法脱硫因操作简单、设备投资省、无二次污染等特点近年来发展迅速，被认为是最具有应用前景的脱硫工艺。所以最近几年干法烟气脱硫技术的研究与开发受到国内外的普遍重视。如果能够采用一种成熟的干法脱硫技术用于烟气二氧化硫的脱除，就可以在降低SO 2排放量的同时，满足各类环保法规要求，保护大气环境。
干法脱硫工艺的核心是吸附剂。干法吸附脱硫吸附剂主要有分子筛和活性炭。分子筛是一种孔径均匀的晶体物质，具有选择吸附特性，可同时脱除H 2S和有机硫，脱后可使硫含量降至15mg/m 3以下，是一种优异的硫化物吸附剂。分子筛吸附剂可以在一定条件下反复再生，使用寿命较长。在环保要求日益严格的新形势下，分子筛脱硫工艺具有广阔的应用前景。
CN104689787A公开了一种液化石油气脱氯吸附剂及其应用方法，其中吸附剂中含有分子筛和具有吸附氯功能的金属氧化物，分子筛的硅铝原子摩尔比为1-45，比表面积为300-650m 2/g，分子筛与具有吸附氯功能的金属氧化物的重量比为45-98:25-50，其中，吸附氯功能的金属氧化物为Na、K、Mg、Ca、Al、镧系金属、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、W、Ru、Rh、Pd、Ag、Cd、Au以及Pt的氧化物中的一种或几种。
CN109277075A公开了一种焦炉煤气净化吸附剂，以吸附剂的重量份数计，包含以下几种组分：
a)5-95份的活性元素改性的疏水分子筛吸附剂A；
b)5-95份的活性元素改性的疏水分子筛吸附剂B；
其中，活性元素选自元素周期表中第ⅠA、ⅡA、ⅤA、ⅠB、ⅡB、ⅢB、ⅣB、ⅤB、ⅥB、ⅦB或第Ⅷ族元素中的至少一种元素；所述的疏水分子筛类吸附剂A中，分子筛选自X 型分子筛、Y型分子筛、A型分子筛、β型分子筛、SAPO型分子筛、MCM-22、MCM-49、MCM-56中的至少一种；所述的疏水分子筛类吸附剂B中，分子筛选自、ZSM型分子筛、丝光沸石、β型分子筛、ZSM-5/丝光沸石、ZSM-5/β沸石、ZSM-5/Y、MCM-22/丝光沸石、ZSM-5/Magadiite、ZSM-5/β沸石/丝光沸石、ZSM-5/β沸石/Y沸石或ZSM-5/Y沸石/丝光沸石中的至少一种。
上述文献虽然报导了分子筛用作吸附剂的技术方案，但未述及其在脱硫中的应用且难以兼顾脱硫率和穿透硫容。因此，基于分子筛开发具有较高硫脱除率以及穿透硫容的吸附剂具有重要的意义。
发明内容
本发明的目的是为了克服现有技术存在的难以兼顾脱硫率和穿透硫容的问题，提供一种分子筛复合物与复合材料及其制备方法和应用。
常规的分子筛吸附剂中大孔或介孔的含量较高，且吸附脱硫的效果较差，本发明的发明人在研究过程中发现，引入铝粘结剂控制分子筛吸附剂中的微孔含量并按照特定含量关系引入特定的金属氧化物，能够显著提高脱硫效果，具体地，使碱土金属的前驱物在铝的前驱物的存在下与具有特定孔分布的稀土改性分子筛以特定比例混捏、焙烧制备分子筛复合物，并使其进一步负载特定的金属助剂能够获得脱硫性能优异的吸附剂，因此，为了实现上述目的，本发明一方面提供了一种分子筛复合物，其特征在于，该分子筛复合物含有铝的氧化物、碱土金属的氧化物和稀土改性分子筛，其中，所述稀土改性分子筛为掺杂有稀土元素的分子筛，所述分子筛复合物中孔径在3nm以下的孔所占的孔体积占总孔体积的百分比≥63.5％；并且该分子筛复合物满足下式I：
Figure PCTCN2020104505-appb-000001
式I中：
W 1表示分子筛复合物中以铝的氧化物计的总铝的重量含量；
W 2表示分子筛复合物中碱土金属的氧化物的重量含量；
W 3表示分子筛复合物中以氧化物计的稀土元素的重量含量；
W 4表示分子筛复合物中以SiO 2计的分子筛的重量含量。
本发明第二方面提供了一种复合材料，该复合材料含有如上所述的分子筛复合物和负载于所述分子筛复合物上的助剂。
本发明第三方面提供了如上所述的分子筛复合物或者复合材料在吸附脱硫中的应用。
本发明第四方面提供了一种具有脱硫功能的系统，该系统包括：
氧化单元，用于处理含硫气体并回收硫磺；
加氢净化单元，与所述氧化单元连接，用于对氧化单元排出的氧化尾气进行加氢还原并回收加氢还原得到的还原产物中的硫化氢；
焚烧单元，用于焚烧加氢净化单元排出的净化尾气；
吸附单元，用于吸附焚烧得到的含SO 2的烟气中的SO 2，吸附单元中使用的吸附剂为如上所述的复合材料。
本发明第五方面提供了一种脱硫的方法，该方法包括：
(a)氧化待处理的含硫气体并回收硫磺；
(b)对氧化后的尾气进行加氢还原并回收加氢还原得到的还原产物中的硫化氢；
(c)焚烧加氢还原后的尾气；
(d)使焚烧得到的含SO 2的烟气与吸附剂接触以吸附SO 2，所述吸附剂为如上所述的复合材料。
本发明与现有技术相比，优点如下：
(1)采用本发明的复合材料作为吸附剂具有较高的饱和硫容和穿透硫容。复合材料的比表面积大于550m 2/g、孔容大于0.25ml/g，保证了复合材料具有良好的吸附性，饱和硫容≥12％，SO 2脱除率降至99％时的硫容(穿透硫容)大于10％，且达穿透硫容时使用的总时间较长。
(2)采用本发明的复合材料具有良好的再生性能，可多次循环使用。
(3)本发明的复合材料制备工艺简单，制备过程无二次污染。
(4)本发明的复合材料可以促进干法脱硫技术的发展，提供一种清洁、无二次污染、符合环保要求的含硫废气治理方法。
附图说明
图1是根据本发明一种优选实施方式的系统的结构示意图；
图2是根据本发明另一种优选实施方式的系统的结构示意图；
图3是根据本发明一种实施方式的复合材料的X-射线衍射图谱；
图4是根据本发明另一种实施方式的复合材料的X-射线衍射图谱。
附图标记说明
11热反应炉                    12一级冷凝器
13一级催化转化器              14二级冷凝器
15二级催化转化器              16三级冷凝器
17液硫池                      21加氢反应器
22加氢尾气冷却器              23急冷塔
24吸收塔                      31焚烧单元
41第一吸附塔                  42第二吸附塔
111尾气再热器                 222烟气换热器
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中，在未作相反说明的情况下，气体的体积以标准状况(STP)(0℃(273K)、1.01×10 5Pa)下的体积表示；“硅铝比”是指硅元素和铝元素之间的摩尔比；的“ppm”是体积浓度单位；压力指表压。“饱和硫容”指单位重量脱硫剂所能吸收硫的最大量，即将新鲜 的吸附剂持续与含硫气体接触，当与吸附剂接触前后的含硫气体的硫含量相等时，吸附剂吸附的硫含量占吸附剂的重量百分比即为饱和硫容。“穿透硫容”指在气体体积空速为1750h -1、反应温度为120℃的条件下，吸附剂在确保工艺净化度指标时(脱除率降至99％时)所能吸收硫的重量百分比。
本发明提供了一种分子筛复合物，其特征在于，该分子筛复合物含有铝的氧化物、碱土金属的氧化物和稀土改性分子筛，其中，所述稀土改性分子筛为掺杂有稀土元素的分子筛，所述分子筛复合物中孔径在3nm以下的孔所占的孔体积占总孔体积的百分比≥63.5％；并且该分子筛复合物满足下式I：
Figure PCTCN2020104505-appb-000002
式I中：
W 1表示分子筛复合物中以铝的氧化物计的总铝的重量含量；
W 2表示分子筛复合物中碱土金属的氧化物的重量含量；
W 3表示分子筛复合物中以氧化物计的稀土元素的重量含量；
W 4表示分子筛复合物中以SiO 2计的分子筛的重量含量。
本发明中，总铝是指铝的氧化物和稀土改性分子筛中提供的铝元素的总和，其含量以Al 2O 3计；碱土金属的氧化物的含量以二价金属氧化物计；稀土元素中，铈的含量以CeO 2计，除铈以外的其他稀土元素的含量以三价金属氧化物计。
根据本发明的分子筛复合物，其中，所述分子筛复合物中孔径在3nm以下的孔所占的孔体积占总孔体积的百分比优选为63.5-72％。
更优选地，所述分子筛复合物中孔径小于2nm的孔所占的孔体积占总孔体积的百分比≥35％，进一步优选为39-45.5％。
更优选地，所述分子筛复合物中孔径为2-3nm的孔所占的孔体积占总孔体积的百分比为20-30％。
更优选地，所述分子筛复合物中孔径大于3nm的孔所占的孔体积占总孔体积的百分比为25-40％。
孔径分布在上述优选范围内的分子筛复合物能够获得更优异脱硫性能的吸附材料。
根据本发明的分子筛复合物，所述铝的氧化物与分子筛之间的重量比优选为(8-35):100，更优选为(12-28):100，如12:100、15:100、18:100、19:100、20:100、25:100、26:100、27:100、28:100或上述数值之间的任意值。其中，分子筛复合物或复合材料中的分子筛的重量百分含量可以根据分子筛复合物或复合材料的相对结晶度进行表征计算。相对结晶度采用XRD方法测定，仪器为Rigaku Dmax-2500X射线衍射仪，采用Cukα辐射，石墨单晶滤波，操作管电压35KV，管电流40mA，扫描速度(2θ)为2°/min，扫描范围为4°-35°；标样为NaY分子筛，硅铝比为5，比表面积为850m 2/g，孔容为0.32ml/g，小于2nm的孔体积占比为32.7％，2-3nm的孔体积占比为22.8％，大于3nm的孔体积占比为44.5％。
根据本发明的分子筛复合物，所述碱土金属的氧化物与分子筛之间的重量比优选为(0.5-3):100，更优选为(0.6-2.1):100，如0.6:100、1:100、1.1:100、1.2:100、1.3:100、1.8:100、1.9:100、2:100、2.1或上述数值之间的任意值。
根据本发明的分子筛复合物，所述稀土元素与分子筛之间的重量比优选为(2.5-10):100， 更优选为(3.7-9.3):100，如3.7:100、4:100、5:100、5.1:100、5.4:100、5.5:100、6:100、6.4:100、6.5:100、6.9:100、7.5:100、7.9:100、8:100、9.2:100、9.3:100或上述数值之间的任意值。
根据本发明，所述铝的氧化物可以为常见的不同价态的铝的氧化物，特别是常见的铝的前驱体经高温焙烧后所得的氧化物。优选地，铝的氧化物为Al 2O 3。
根据本发明，所述碱土金属的氧化物可以为常见的不同价态的碱土金属(如铍(Be)、镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镭(Ra))的氧化物，特别是常见的碱土金属的前驱体经高温焙烧后所得的氧化物。优选地，碱土金属的氧化物为CaO、MgO和BaO中的至少一种。
根据本发明，所述稀土元素可以为常见的稀土元素，如镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钇(Y)和钪(Sc)。优选地，稀土元素为Ce和/或La。进一步优选地，所述稀土元素为Ce和La且Ce与La的重量比为1-3。选择优选的稀土元素的氧化物能够进一步提高基于所述分子筛复合物制得的复合材料的吸附性能。
根据本发明，所述稀土改性分子筛可以为常规的经稀土改性的分子筛，特别是稀土改性Y型分子筛，优选为稀土改性NaY分子筛。在所述稀土改性分子筛中，稀土元素以阳离子的形式键合至分子筛的孔道中。
根据本发明的优选实施方式，所述分子筛复合物的比表面积≥550m 2/g，更优选为550-600m 2/g。
根据本发明的优选实施方式，所述分子筛复合物的孔容≥0.25ml/g，更优选为0.25-0.4ml/g。
本发明提供了一种制备分子筛复合物的方法，其特征在于，该方法包括：在溶剂存在的条件下，将铝的前驱体、碱土金属的前驱体、稀土改性分子筛和可选的非金属粘结剂进行混捏、成型、干燥和焙烧，其中，所述稀土改性分子筛为掺杂有稀土元素的分子筛，所述铝的前驱体、碱土金属的前驱体和稀土改性分子筛的用量使所得分子筛复合物中铝元素、碱土金属元素、稀土元素和分子筛之间的含量满足式I，其中，铝元素、碱土金属元素和稀土元素的重量以氧化物计。
根据本发明的制备分子筛复合物的方法，所述铝的前驱体和稀土改性分子筛的用量使所得分子筛复合物中铝元素与分子筛之间的重量比优选为(8-35):100，更优选为(12-28):100。
根据本发明的制备分子筛复合物的方法，所述碱土金属的前驱体和稀土改性分子筛的用量使所得分子筛复合物中碱土金属元素与分子筛之间的重量比优选为(0.5-3):100，更优选为(0.6-2.1):100。
根据本发明的制备分子筛复合物的方法，所述稀土元素的用量使所得分子筛复合物中稀土元素和分子筛之间的重量比优选为(2.5-10):100，更优选为(3.7-9.3):100。
根据本发明，对铝的前驱体没有特别的限制，但优选地，所述铝的前驱体为铝的氧化物和/或铝的氢氧化物，更优选为氢氧化铝和/或拟薄水铝石。
根据本发明，对所述碱土金属的前驱体没有特别的要求，优选地，碱土金属的前驱体为碱土金属的氧化物、碱土金属的氢氧化物、碱土金属的碳酸盐和碱土金属的硝酸盐中的至少一种，更优选为氧化钙、碳酸钙、硝酸钙、氧化镁、碳酸镁、硝酸镁、硝酸钡、氧化钡和碳酸钡中的至少一种。
根据本发明，所述稀土元素可以为常见的稀土元素，如镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钇(Y)和钪(Sc)。优选地，稀土元素为Ce和/或La。进一步优选地，所述稀土元素为Ce和La且Ce与La的重量比为1-3。选择优选的稀土元素的氧化物能够进一步提高最终制备的复合材料的吸附性能。
根据本发明，所述稀土改性分子筛可以为常规的经稀土改性的分子筛，特别是稀土改性Y型分子筛，优选为稀土改性NaY分子筛。在所述稀土改性分子筛中，稀土元素以阳离子的形式键合至分子筛的孔道中。
根据本发明，所述非金属粘结剂为选择性使用的物质，非金属粘结剂的使用有利于分子筛复合物的成型。对所述非金属粘结剂的用量没有特别的要求，但优选地，所述分子筛与非金属粘结剂的重量比为100:(1-3)。
根据本发明，所述非金属粘结剂可以为已有的各种不含金属元素的粘结剂，优选地，所述非金属粘结剂为有机酸和/或无机酸，进一步优选为硝酸、盐酸、硫酸和柠檬酸中的至少一种。
根据本发明，所述稀土改性分子筛可以通过常规的方式获得，例如，所述稀土改性分子筛的制备方法包括：在pH＝3-5的条件下，将分子筛与水溶性稀土金属盐混合(进行离子交换)。优选地，所述分子筛的硅铝比为2-10，更优选为4.5-7。优选地，所述分子筛的比表面积≥600m 2/g，更优选为700-1000m 2/g。优选地，所述分子筛的孔容≥0.3ml/g，更优选为0.3-0.35ml/g。更优选地，所述分子筛为NaY分子筛。所述分子筛中，孔径小于2nm的孔所占的孔体积占总孔体积的百分比优选为20-35％，孔径为2-3nm的孔所占的孔体积占总孔体积的百分比优选为10-26％，孔径大于3nm的孔所占的孔体积占总孔体积的百分比优选为40-65％。所述水溶性稀土金属盐可以为各种溶于水产生稀土金属离子的物质，优选地，所述水溶性稀土金属盐为稀土金属的硝酸盐和/或稀土金属的氯化物，更优选为硝酸铈、氯化铈、硝酸镧和氯化镧中的至少一种。对所述混合的条件没有特别的限制，但优选地，所述混合的条件包括：温度为70-90℃。优选地，所述混合的条件还包括：时间为20min-3h。为了提高稀土改性分子筛中稀土元素的含量(提高稀土离子的交换深度)，所述方法还可以包括对混合后所得的产物进行干燥和焙烧(500-600℃，3-6h)，并再在pH＝3-5的条件下，将分子筛与水溶性稀土金属盐混合(进行二次交换)。
根据本发明的制备分子筛复合物的方法，所述干燥的条件可以包括：干燥温度为100-160℃，优选为110-130℃。所述干燥的条件还可以包括：干燥时间为4-6h。
根据本发明的制备分子筛复合物的方法，所述焙烧的条件可以包括：焙烧温度为400-700℃，优选为450-600℃。所述焙烧的条件还可以包括：焙烧时间为3-8h，优选为4-6h。
根据本发明的制备分子筛复合物的方法，对溶剂没有特别的要求，可以为常见的有机溶剂和/或无机溶剂。但优选情况下，所述溶剂为水。本领域技术人员可以根据混捏和成型的要求控制溶剂的用量，在此不再赘述。
根据本发明的制备分子筛复合物的方法，可以采用常规的方式进行混捏、成型，例如，可以借助成型设备，如挤条机等。
本发明还提供了由如上所述的方法制得的分子筛复合物。
本发明提供了一种复合材料，其特征在于，该复合材料含有如上所述的分子筛复合物和负载于所述分子筛复合物上的助剂。
根据本发明的复合材料，所述复合材料中孔径在3nm以下的孔所占的孔体积占总孔体积的百分比优选≥65％，更优选为65-75％。
更优选地，所述复合材料中孔径小于2nm的孔所占的孔体积占总孔体积的百分比≥45％，进一步优选为45-55％。
更优选地，所述复合材料中孔径为2-3nm的孔所占的孔体积占总孔体积的百分比为15-35％。
更优选地，所述复合材料中孔径大于3nm的孔所占的孔体积占总孔体积的百分比为20-35％。
孔径分布在上述优选范围内的复合材料具有更优异的脱硫性能。
优选地，所述复合材料具有基本上如图3所示的X-射线衍射图谱。所述复合材料具有基本上如下表1-a所示的X-射线衍射图谱：
表1-a
Figure PCTCN2020104505-appb-000003
由此可见，所述复合材料与未改性分子筛的XRD谱图相似，并未发现其他氧化物的特征衍射峰。这说明改性分子筛均保持分子筛原有的结构，并没有新增结构出现。稀土金属的引入并没有破坏分子筛的骨架结构，且稀土金属在分子筛上处于均匀分散状态。此外，与分子筛相比，稀土金属等改性的分子筛的特征衍射峰明显下降，这是因稀土金属氧化物较高的吸收系数造成的。
根据本发明，助剂和分子筛之间的重量比优选为(0.8-4):100，更优选为(1.2-3.3):100，如1.2:100、1.5:100、1.8:100、2:100、2.5:100、2.6:100、2.7:100、2.8:100、3:100、3.3:100或上述数值之间的任意值。
根据本发明，所述助剂可以为现有的具有辅助脱硫功能的金属氧化物，如VIB族或VIII族金属的氧化物，特别地，所述助剂优选为镍的氧化物、钴的氧化物和钼的氧化物中的至少一种。
根据本发明，所述镍的氧化物可以为常见的不同价态的镍的氧化物，特别是常见的镍的前驱体经高温焙烧后所得的氧化物。优选地，镍的氧化物为NiO。
根据本发明，所述钴的氧化物可以为常见的不同价态的钴的氧化物，特别是常见的钴的 前驱体经高温焙烧后所得的氧化物。优选地，钴的氧化物CoO。
根据本发明，所述钼的氧化物可以为常见的不同价态的钼的氧化物，特别是常见的钼的前驱体经高温焙烧后所得的氧化物。优选地，钼的氧化物为MoO 3。
根据本发明的优选实施方式，所述复合材料的比表面积≥550m 2/g，更优选为558-580m 2/g。
根据本发明的优选实施方式，所述复合材料的孔容≥0.25ml/g，更优选为0.26-0.3ml/g。
根据本发明的优选实施方式，所述复合材料的饱和硫容≥12％，更优选为12-15％。
根据本发明的优选实施方式，所述复合材料的穿透硫容≥10％，更优选为10-11％。
根据本发明的优选实施方式，本发明的分子筛复合物或复合材料不含可检测量的Sc、Ti、V、Cr、Mn、Fe、Cu、Zn、W、Ru、Rh、Pd、Ag、Cd、Au、Y或Pt。更优选地，本发明的分子筛复合物或复合材料仅由如上所述的成分组成。
本发明提供了一种制备复合材料的方法，其特征在于，该方法包括：
(1)在溶剂存在的条件下，将铝的前驱体、碱土金属的前驱体、稀土改性分子筛和可选的非金属粘结剂进行混捏、成型、干燥和焙烧，得到分子筛复合物，其中，所述稀土改性分子筛为掺杂有稀土元素的分子筛，所述铝的前驱体、碱土金属的前驱体和稀土改性分子筛的用量使所得分子筛复合物中铝元素、碱土金属元素、稀土元素和分子筛用量之间的关系满足式I；
(2)将助剂的前驱体与所述分子筛复合物接触，以使分子筛复合物负载上助剂，其中，所述助剂的前驱体为镍的前驱体、钴的前驱体和钼的前驱体中的至少一种，所述助剂的前驱体的用量使所得复合材料中助剂与分子筛之间的重量比为(0.8-4):100；
其中，铝元素、碱土金属元素、稀土元素和助剂的重量以氧化物计。
根据本发明的方法，所述铝的前驱体和稀土改性分子筛的用量使所得分子筛复合物中铝元素与分子筛之间的重量比优选为(8-35):100，更优选为(12-28):100，如12:100、15:100、18:100、19:100、20:100、25:100、26:100、27:100、28:100或上述数值之间的任意值。
根据本发明的方法，所述碱土金属的前驱体和稀土改性分子筛的用量使所得分子筛复合物中碱土金属元素与分子筛之间的重量比优选为(0.5-3):100，更优选为(0.6-2.1):100，如0.6:100、1:100、1.1:100、1.2:100、1.3:100、1.8:100、1.9:100、2:100、2.1或上述数值之间的任意值。
根据本发明的方法，所述稀土元素的用量使所得分子筛复合物中稀土元素和分子筛之间的重量比优选为(2.5-10):100，更优选为(3.7-9.3):100，如3.7:100、4:100、5:100、5.1:100、5.4:100、5.5:100、6:100、6.4:100、6.5:100、6.9:100、7.5:100、7.9:100、8:100、9.2:100、9.3:100或上述数值之间的任意值。
根据本发明的方法，所述助剂的前驱体的用量使所得复合材料中助剂与分子筛之间的重量比优选为(1.2-3.3):100，如1.2:100、1.5:100、1.8:100、2:100、2.5:100、2.6:100、2.7:100、2.8:100、3:100、3.3:100或上述数值之间的任意值。
根据本发明，对铝的前驱体没有特别的限制，但优选地，所述铝的前驱体为铝的氧化物和/或铝的氢氧化物，更优选为氢氧化铝和/或拟薄水铝石。
根据本发明，对所述碱土金属的前驱体没有特别的要求，优选地，碱土金属的前驱体为碱土金属的氧化物、碱土金属的氢氧化物、碱土金属的碳酸盐和碱土金属的硝酸盐中的至少 一种，更优选为氧化钙、碳酸钙、硝酸钙、氧化镁、碳酸镁、硝酸镁、硝酸钡、氧化钡和碳酸钡中的至少一种。
根据本发明，所述稀土元素可以为常见的稀土元素，如镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钇(Y)和钪(Sc)。优选地，稀土元素为Ce和/或La。进一步优选地，所述稀土元素为Ce和La且Ce与La的重量比为1-3。选择优选的稀土元素的氧化物能够进一步提高最终制备的复合材料的吸附性能。
根据本发明，所述稀土改性分子筛可以为常规的经稀土改性的分子筛，特别是稀土改性Y型分子筛，优选为稀土改性NaY分子筛。在所述稀土改性分子筛中，稀土元素以阳离子的形式键合至分子筛的孔道中。
根据本发明，所述非金属粘结剂为选择性使用的物质，非金属粘结剂的使用有利于分子筛复合物的成型。对所述非金属粘结剂的用量没有特别的要求，但优选地，所述分子筛与非金属粘结剂的重量比为100:(1-3)。
根据本发明，所述非金属粘结剂可以为已有的各种不含金属元素的粘结剂，优选地，所述非金属粘结剂为有机酸和/或无机酸，进一步优选为硝酸、盐酸、硫酸和柠檬酸中的至少一种。
根据本发明，所述稀土改性分子筛可以通过常规的方式获得，例如，所述稀土改性分子筛的制备方法包括：在pH＝3-5的条件下，将分子筛与水溶性稀土金属盐混合(进行离子交换)。优选地，所述分子筛的硅铝比为2-10，更优选为4.5-7。优选地，所述分子筛的比表面积≥600m 2/g，更优选为700-1000m 2/g。优选地，所述分子筛的孔容≥0.3ml/g，更优选为0.3-0.35ml/g。更优选地，所述分子筛为NaY分子筛。所述分子筛中，孔径小于2nm的孔所占的孔体积占总孔体积的百分比优选为20-35％，孔径为2-3nm的孔所占的孔体积占总孔体积的百分比优选为10-26％，孔径大于3nm的孔所占的孔体积占总孔体积的百分比优选为40-65％。所述水溶性稀土金属盐可以为各种溶于水产生稀土金属离子的物质，优选地，所述水溶性稀土金属盐为稀土金属的硝酸盐和/或稀土金属的氯化物，更优选为硝酸铈、氯化铈、硝酸镧和氯化镧中的至少一种。对所述混合的条件没有特别的限制，但优选地，所述混合的条件包括：温度为70-90℃。优选地，所述混合的条件还包括：时间为20min-3h。为了提高稀土改性分子筛中稀土元素的含量(提高稀土离子的交换深度)，所述方法还可以包括对混合后所得的产物进行干燥和焙烧(500-600℃，3-6h)，并再在pH＝3-5的条件下，将分子筛与水溶性稀土金属盐混合(进行二次交换)。
根据本发明，所述干燥的条件可以包括：干燥温度为100-160℃，优选为110-130℃。所述干燥的条件还可以包括：干燥时间为4-6h。
根据本发明，所述焙烧的条件可以包括：焙烧温度为400-700℃，优选为450-600℃。所述焙烧的条件还可以包括：焙烧时间为3-8h，优选为4-6h。
根据本发明，所述助剂的前驱体为可溶性镍盐、可溶性钴盐和可溶性钼盐中的至少一种，优选为硝酸镍、硝酸钴、硝酸钼、氯化镍、氯化钴和氯化钼、硫酸镍、硫酸钴和硫酸钼中的至少一种。
根据本发明，步骤(1)中，所述干燥的条件可以包括：干燥温度为100-160℃，优选为 110-130℃。所述干燥的条件还可以包括：干燥时间为4-6h。
根据本发明，步骤(1)中，所述焙烧的条件可以包括：焙烧温度为400-700℃，优选为450-600℃。所述焙烧的条件还可以包括：焙烧时间为3-8h，优选为4-6h。
根据本发明，步骤(2)中，可以采用常规的方法使分子筛复合物负载上助剂，优选情况下，使分子筛复合物负载上助剂的方式为：用含有助剂的前驱体的溶液对分子筛复合物进行等体积浸渍，干燥浸渍物，并将干燥产物进行焙烧。
更优选地，等体积浸渍的条件包括：温度为5-40℃，进一步优选为20-30℃。更优选地，等体积浸渍的条件还包括：时间为20min-2.5h，进一步优选为0.5-1h。
更优选地，干燥浸渍物的条件包括：温度为80-160℃，进一步优选为110-130℃。更优选地，干燥浸渍物的条件还包括：时间为2-10h，进一步优选为4-6h。
更优选地，将干燥产物进行焙烧的条件包括：焙烧温度为300-500℃，进一步优选为350-450℃。更优选地，将干燥产物进行焙烧的条件还包括：焙烧时间为2-10h，进一步优选为3-5h。
根据本发明的方法，对溶剂没有特别的要求，可以为常见的有机溶剂和/或无机溶剂。但优选情况下，所述溶剂为水。本领域技术人员可以根据混捏和成型的要求控制溶剂的用量，在此不再赘述。
根据本发明的方法，可以采用常规的方式进行混捏、成型，例如，可以借助成型设备，如挤条机等。
本发明还提供了由如上所述的方法制得的复合材料。
本发明还提供了如上所述的改性活性炭或者复合材料在吸附脱硫中的应用，尤其是在对硫含量较低的样品(如二氧化硫含量不高于0.2体积％(即6000mg/m 3)的气体样品，例如烟气)进行吸附脱硫中的应用。
本发明还提供了一种脱硫的方法，其特征在于，该方法包括：将待处理的含硫气体与如上所述的复合材料进行接触；
或者，该方法包括：按照如上所述的方法制备复合材料；再将含硫气体与所得复合材料进行接触。
根据本发明的脱硫方法特别适用于硫含量较低的样品中硫的脱除，因此，优选地，所述含硫气体中二氧化硫的含量不高于0.2体积％。另一方面，当所述含硫气体中二氧化硫的含量高于0.2体积％时，所述方法优选还包括在与复合材料接触之前使含硫气体中二氧化硫的含量降低至0.2体积％以下。
根据本发明的脱硫方法，对接触的条件没有特别的要求，但优选地，所述接触的条件包括：温度为100-150℃。优选地，所述接触的条件还包括：气体体积空速为1500-2000h -1。
根据本发明，所述复合材料不仅具有良好的吸附性，还具有优异的再生性能。因此，所述方法还包括：对所述复合材料进行再生。对再生的方法没有特别的要求，例如，所述再生的方式可以为热再生和/或水洗再生。可以采用常规的条件对本发明的复合材料进行热再生和/或水洗再生。
更优选地，所述热再生的方式为气体吹扫，气体吹扫的条件包括：气体体积空速为1000-1500h -1，温度为150-250℃，吹扫的气体为非活性气体(如氮气)。
更优选地，所述水洗再生的条件包括：液时空速为0.5-1.5h -1，温度为25-40℃。
根据本发明的脱硫方法，所述含硫气体为石油炼制工业加热炉烟气、硫磺尾气和催化裂化再生烟气中的至少一种。
本发明还提供了一种具有脱硫功能的系统，其特征在于，该系统包括：
氧化单元，用于处理含硫气体并回收硫磺；
加氢净化单元，与所述氧化单元连接，用于对氧化单元排出的氧化尾气进行加氢还原并回收加氢还原得到的还原产物中的硫化氢；
焚烧单元，用于焚烧加氢净化单元排出的净化尾气；
吸附单元，用于吸附焚烧得到的含SO 2的烟气中的SO 2，吸附单元中使用的吸附剂为如上所述的复合材料。
根据本发明的系统，为了便于再生吸附单元中的复合材料，所述吸附单元包括再生物的入口和出口，从而方便将再生物(热源或水洗水)引入吸附单元对复合材料进行再生。所述吸附单元还优选进一步与氧化单元相连，使得再生得到的含SO 2的再生气返回氧化单元进行再处理。
根据本发明的系统，为了实现系统的连续运行，优选地，所述吸附单元包括至少两个吸附塔(如第一吸附塔41和第二吸附塔42)，用于交替使用以连续吸附焚烧得到的含SO 2的烟气中的SO 2。当采用热再生的方式对复合材料进行再生时，如图1所示，热气(如热氮)可以从吸附塔的底部引入，产生的再生气从吸附塔的顶部排出，可以进一步引入氧化单元进行再处理。当采用水洗再生的方式对复合材料再生时，如图2所示，水洗水可以从吸附塔的顶部引入，产生的再生稀酸从吸附塔的底部排出，可以进一步引入氧化单元进行再处理。
根据本发明的系统，所述氧化单元可以包括液硫池17和依次连接的热反应炉11、一级冷凝器12和催化转化器，所述液硫池17与一级冷凝器12和催化转化器相连，用于收集冷却后的液体硫磺。为了更有效地回收硫磺，优选地，所述氧化单元包括液硫池17和依次连接的热反应炉11、一级冷凝器12、一级催化转化器13、二级冷凝器14、二级催化转化器15和三级冷凝器16，所述液硫池17分别与一级冷凝器12、二级冷凝器14和三级冷凝器16相连，用于收集冷却后的液体硫磺。
根据本发明的系统，所述加氢净化单元可以包括依次连接的加氢反应器21、加氢尾气冷却器22、急冷塔23和吸收塔24。氧化单元排出的氧化尾气在加氢反应器21中进行加氢还原，然后进入加氢尾气冷却器22和急冷塔23中被冷却，再进入吸收塔24中吸收还原产物中的硫化氢。
根据本发明的系统，所述焚烧单元可以为焚烧炉和/或催化焚烧反应器。
根据本发明的系统，所述氧化单元、加氢净化单元和焚烧单元用于降低含硫气体中的硫(主要包括硫化氢)含量，而设置有吸附材料的吸附单元用于进一步降低二氧化硫的含量。
本发明还提供了一种脱硫的方法，其特征在于，该方法包括：
(a)氧化待处理的含硫气体并回收硫磺；
(b)对氧化后的尾气进行加氢还原并回收加氢还原得到的还原产物中的硫化氢；
(c)焚烧加氢还原后的尾气；
(d)使焚烧得到的含SO 2的烟气与吸附剂接触以吸附SO 2，所述吸附剂为如上所述的复 合材料。
根据本发明，步骤(d)中，对接触的条件没有特别的要求，但优选地，所述接触的条件包括：温度为100-150℃。优选地，所述接触的条件还包括：气体体积空速为1500-2000h -1。
根据本发明，所述复合材料不仅具有良好的吸附性，还具有优异的再生性能。因此，所述方法还包括对吸附剂进行再生。对再生的方法没有特别的要求，例如，所述再生的方式可以为热再生和/或水洗再生。可以采用常规的条件对本发明的复合材料进行热再生和/或水洗再生。为了进一步确保硫的零排放，所述方法还包括对吸附剂进行再生，并将再生得到的含SO 2的再生气返回步骤(a)进行再处理。
更优选地，所述热再生的方式为气体吹扫，气体吹扫的条件包括：气体体积空速为1000-1500h -1，温度为150-250℃，吹扫的气体为非活性气体(如氮气)。
更优选地，所述水洗再生的条件包括：液时空速为0.5-1.5h -1，温度为25-40℃。
对于再生的时间，本领域技术人员能够对其进行选择，只要能够使再生后的复合材料的硫容恢复至原始状态的95％以上即可。
根据本发明，对步骤(a)中的氧化没有特别的要求，只要能够使含硫气体发生克劳斯反应从而得到硫磺即可。例如，氧化的方式可以为：将含硫气体依次进行燃烧、一级冷却和催化反应。
优选地，所述燃烧的条件包括：温度为900-1400℃，停留时间为2-3s。本发明中，“停留时间”是指含硫气体在燃烧容器内的停留时间，即气体从进炉到出炉的时间，也就是气体的反应时间。
优选地，所述一级冷却的条件使得冷却后的气体的温度为120-180℃。
优选地，所述催化反应的条件包括：催化剂为氧化铝基催化剂和/或氧化钛基催化剂，气体体积空速为500-1000h -1，温度为200-350℃。
更优选地，所述催化反应的方式为依次进行一级催化反应、二级冷却、二级催化反应和三级冷却。进一步优选地，所述一级催化反应的条件包括：催化剂为氧化铝基催化剂和/或氧化钛基催化剂，气体体积空速为600-800h -1，温度为290-330℃。进一步优选地，所述二级冷却的条件使得冷却后的气体的温度为130-160℃。进一步优选地，所述二级催化反应的条件包括催化剂为氧化铝基催化剂，气体体积空速为600-800h -1，温度为220-250℃。进一步优选地，所述三级冷却的条件使得冷却后的气体的温度为130-160℃。
本发明中，氧化铝基催化剂的主要成分为Al 2O 3，比表面积≥350m 2/g，孔容≥0.45ml/g，可以通过商购获得，例如，购自山东齐鲁科力化工研究院有限公司的LS-02催化剂。氧化钛基催化剂的主要成分为TiO 2，比表面积≥180m 2/g，孔容≥0.3ml/g，可以通过商购获得，例如，购自山东齐鲁科力化工研究院有限公司的LS-981催化剂。
根据本发明，步骤(b)中，所述加氢还原的条件可以包括：加氢催化剂为Co-Mo系尾气加氢催化剂，气体体积空速为500-1000h -1，温度为220-350℃。优选地，回收加氢还原得到的还原产物中的硫化氢的方式为：使加氢还原得到的还原产物降温至30-40℃，并使用胺液吸收降温后的产物中的硫化氢。胺液中胺的浓度可以为20-50重量％。所述胺液中的胺可以为各种醇胺类脱硫剂，其中优选甲基二乙醇胺(MDEA)。所述胺液可以为淄博凯美可工贸有限公司的KMKTS-15高效脱硫剂。
本发明中，Co-Mo系尾气加氢催化剂可以是以改性Al 2O 3为载体，以钴、钼等为活性金属组份的克劳斯尾气低温加氢催化剂，比表面积≥200m 2/g，可以通过商购获得，例如，购自山东齐鲁科力化工研究院有限公司的LSH-02催化剂。Co-Mo系尾气加氢催化剂还可以是以改性Al 2O 3为载体，以钴、钼为活性金属组份的克劳斯尾气加氢专用催化剂，比表面积≥300m 2/g，可以通过商购获得，例如，购自山东齐鲁科力化工研究院有限公司的LS-951T催化剂。
根据本发明，步骤(c)中，所述焚烧的条件可以包括温度为600-800℃，停留时间为2-3s。
根据本发明，步骤(c)中，所述焚烧可以为常规的焚烧方式。优选地，所述焚烧的方式为催化焚烧，所述催化焚烧的条件包括：催化剂为含有铁和钒的催化焚烧催化剂，温度为250-350℃，空速为500-1000h -1。所述含有铁和钒的催化焚烧催化剂的具体组成为：Fe 2O 3 2-8重量％，V 2O 5为1-4重量％，余量为白炭黑。
根据本发明，所述含硫气体中CO 2的含量为3-5％、SO 2的体积含量为20-1000ppm、NOx的体积含量为20-150ppm、O 2的含量为3-5％、H 2O的含量为3-10重量％。
根据本发明，所述方法在如上所述的系统中的实施。
实施例
以下将通过实施例对本发明进行详细描述。以下实施例中：
分子筛原粉购自中国石化催化剂有限公司齐鲁分公司；
碱性硅溶胶购自青岛中能硅化工有限公司；
氢氧化铝干胶购自扬州帝蓝化工原料有限公司；
拟薄水铝石购自山东省德州市晶火技术玻璃有限公司；
挤条机的型号为ZYDJ-30，厂家为淄博悦诚机械有限公司；
元素组成的测定方法为X射线荧光法，具体检测参照GB/T 30905-2014，并结合X射线光电子能谱分析确定元素的价态；表2和表3中分子筛与Al 2O 3以投料量示出；
孔体积占比、比表面积和孔容的检测方法参照GB/T6609.35-2009；
XRD谱图的测试方法参照：Q/SH3160.R064-2007。
实施例1
称取800g的分子筛原粉(NaY分子筛，硅铝比为5，比表面积为850m 2/g，孔容为0.32ml/g，小于2nm的孔体积占比为32.7％，2-3nm的孔体积占比为22.8％，大于3nm的孔体积占比为44.5％)置于烧杯中，加入蒸馏水，使水/分子筛重量比达到8左右。称取76g氯化铈(CeCl 3·6H 2O)、30g氯化镧(LaCl 3)制成氯化稀土溶液。将氯化稀土溶液加入烧杯中搅拌均匀，用盐酸调pH值为4左右，把烧杯置于水浴中加热至80℃左右，在搅拌的状态下交换1小时，交换过程结束。冷却、过滤、洗涤、烘干。为了提高稀土离子的交换深度，对首次交换后的分子筛进行焙烧，在550℃下焙烧4小时。焙烧后，按上述方法对分子筛进行二次交换，得到改性分子筛。
将所得改性分子筛、氢氧化铝干胶(330g，固含量70重量％，比表面积为450m 2/g，孔容为0.9mL/g)和氧化钙10g，去离子水450g混合均匀，加入12g硝酸作为粘结剂，在挤条 机上挤条成型，得到
Figure PCTCN2020104505-appb-000004
的长条形物料，所得长条物料在120℃下干燥4h，然后在500℃下焙烧4h，得到分子筛复合物(或吸附剂载体)，对其比表面积和孔容进行测定，结果见表4。
取78g硝酸镍(Ni(NO 3)·6H 2O)将其溶解，根据制得分子筛复合物的吸水率进行定容，使之形成稳定的共浸液。取共浸液等体积浸渍吸附剂载体，浸渍温度为25℃，浸渍时间为1h，浸渍后的物料在120℃干燥6小时、450℃焙烧4h，制得吸附剂，吸附剂的元素组成(单位：重量％)测定结果见表2，比表面积和孔容的测定结果见表4。所得吸附剂的XRD谱图数据如表2-1所示，XRD谱图如图3所示。
实施例2-7
按照实施例1的各个步骤与条件制备吸附剂，只是改变组成、制备条件或浸渍溶液浓度，具体制备条件见表1，最终制得的吸附剂产品中各个金属氧化物和分子筛的含量(重量百分比)如表2所示，比表面积等的测定结果见表4。所得吸附剂的XRD谱图数据如表2-2至表2-7所示，XRD谱图均与图3相似。
表1
Figure PCTCN2020104505-appb-000005
表2
Figure PCTCN2020104505-appb-000006
表2-1
Figure PCTCN2020104505-appb-000007
表2-2
Figure PCTCN2020104505-appb-000008
表2-3
Figure PCTCN2020104505-appb-000009
表2-4
Figure PCTCN2020104505-appb-000010
表2-5
Figure PCTCN2020104505-appb-000011
表2-6
Figure PCTCN2020104505-appb-000012
表2-7
Figure PCTCN2020104505-appb-000013
实施例8
按照实施例1的各个步骤与条件制备吸附剂，只是将硝酸镍替换为等重量(以金属氧化物计)的硝酸钴，比表面积等的测定结果见表4。所得吸附剂的XRD谱图数据如表2-8所示。
表2-8
Figure PCTCN2020104505-appb-000014
Figure PCTCN2020104505-appb-000015
实施例9
按照实施例1的各个步骤与条件制备吸附剂，只是将硝酸镍替换为等重量(以金属氧化物计)的硝酸钼，比表面积等的测定结果见表4。所得吸附剂的XRD谱图数据如表2-9所示。
表2-9
Figure PCTCN2020104505-appb-000016
实施例10
按照实施例2的各个步骤与条件制备吸附剂，只是将NaY分子筛替换为13X分子筛(购自天津市大茂化学试剂厂，比表面积为724m 2/g，孔容为0.34ml/g，小于2nm的孔体积占比为28.5％，2-3nm的孔体积占比为26％，大于3nm的孔体积占比为45.5％)，比表面积等的测定结果见表4。
所得吸附剂的XRD谱图数据如表2-10所示，XRD谱图如图4所示。
表2-10
Figure PCTCN2020104505-appb-000017
Figure PCTCN2020104505-appb-000018
参比实施例1-8
按照实施例1的各个步骤与条件制备吸附剂，只是改变了浸渍溶液浓度，使得最终制得的吸附剂产品中各个金属氧化物和分子筛的含量(单位：重量％)如表3所示，比表面积等的测定结果见表4。
表3
Figure PCTCN2020104505-appb-000019
参比实施例9-10
按照实施例1的各个步骤与条件制备吸附剂，不同的是，将硝酸镍替换为等重量(以金属氧化物计)的硝酸铁和硝酸锌，比表面积等的测定结果见表4。
参比实施例11
按照实施例1的各个步骤与条件制备吸附剂，不同的是，将氯化镧和氯化铈替换为等重量的硝酸镍，比表面积等的测定结果见表4。
参比实施例12
按照实施例1的各个步骤与条件制备吸附剂，不同的是，将氧化钙替换为等重量(以金属氧化物计)的氧化钠，比表面积等的测定结果见表4。
参比实施例13
按照实施例1的各个步骤与条件制备吸附剂，不同的是，将氢氧化铝干胶替换为等重量的碱性硅溶胶，比表面积等的测定结果见表4。
参比实施例14
按照实施例1的各个步骤与条件制备吸附剂，不同的是，不预先制备稀土改性分子筛，而将氯化铈和氯化镧与硝酸镍一起形成共浸液等体积浸渍吸附剂载体，具体步骤如下：
将800g分子筛原粉、氢氧化铝干胶和氧化钙10g，去离子水450g混合均匀，加入12g硝酸作为粘结剂，在挤条机上挤条成型，得到
Figure PCTCN2020104505-appb-000020
的长条形物料，所得长条物料在120℃下干燥4h，然后在500℃下焙烧4h，得到分子筛复合物(或吸附剂载体)。
取78g硝酸镍(Ni(NO 3)·6H 2O)、76g氯化铈、30g氯化镧，将其溶解，根据制得分子筛复合物的吸水率进行定容，使之形成稳定的共浸液。取共浸液等体积浸渍吸附剂载体，浸渍温度为25℃，浸渍时间为1h，浸渍后的物料在120℃干燥6小时、450℃焙烧4h。
表4
Figure PCTCN2020104505-appb-000021
Figure PCTCN2020104505-appb-000022
测试例1
对实施例和参比实施例制备的吸附剂进行吸附活性评价：
微反装置的反应器由内径为20mm的不锈钢管制成，反应器放置在恒温箱内。吸附剂装填量为10ml，上部装填相同粒度的石英砂进行混合预热。采用AC公司生产的形态硫色谱仪分析反应器入口及出口气体中SO 2的含量。
色谱操作条件如下：
色谱柱：安捷伦7890B
检测器：Antek 7090(SCD)
色谱柱：不锈钢柱长30m，内径0.32mm，液膜厚度4μm；液膜规格PDMS-1
柱温度：250℃
检测器温度：950℃
气化室温度：275℃
载气(N 2)流速：90ml/min；
进样量：1μL
入口气体体积组成为CO 2 3体积％、SO 2 0.03体积％(900mg/m 3)、H 2O 3体积％，其余为N 2，气体体积空速为1750h -1，反应温度为120℃。
根据下式计算吸附剂对SO 2的脱除率ηSO 2：
Figure PCTCN2020104505-appb-000023
其中N 0和N 1则分别代表入口及出口处SO 2的体积浓度。
根据下式计算硫容：
Figure PCTCN2020104505-appb-000024
其中M 硫表示吸附剂吸附硫的重量，M 催表示用于吸附硫的吸附剂的重量；饱和硫容指单位重量脱硫剂所能吸收硫的最大量，即将新鲜的吸附剂持续与含硫气体接触，当与吸附剂接触前后的含硫气体的硫含量相等时，吸附剂吸附的硫含量占吸附剂的百分比即为饱和硫容。
穿透硫容：在一定使用条件下，吸附剂在确保工艺净化度指标时所能吸收硫的重量百分比。换言之，即当出口工艺气中硫含量出现大于工艺净化度指标时，立即卸下全部废催化剂，取平均样测定的硫容叫穿透硫容。本发明中，SO 2脱除率降至99％时即认为达到穿透，即本发明中的穿透硫容是指SO 2脱除率降至99％时吸附剂的硫容，达穿透硫容时吸附剂使用的总时间定义为吸附时长。
分析结果见表5。
表5
Figure PCTCN2020104505-appb-000025
Figure PCTCN2020104505-appb-000026
测试例2
对实施例1和参比实施例1、4和5制备的吸附剂进行脱除SO 2试验(具体方法同测试例1)，当吸附剂对SO 2的吸附发生穿透，达到吸附剂的穿透硫容时，停止对含SO 2气体的吸附，转换氮气对吸附剂进行再生性能考察。再生条件为：空速1200h -1，温度为200℃，吹扫气体为氮气，再生时间为6h。用再生后的吸附剂进行脱除SO 2试验，达穿透硫容时又进行再生，对吸附剂连续进行了5次再生，每次再生后的吸附剂SO 2穿透硫容结果见表6。
表6
Figure PCTCN2020104505-appb-000027
从表6中的数据可以看出：本发明实施例穿透硫容基本保持不变，本发明的复合材料表现出良好的再生性能。进一步的实验证明，实施例2-7所得的吸附剂的再生性能与实施例1类似(结果未示出)。
测试例3
使用本发明的系统进行脱硫，如图1所示，所述系统包括：
氧化单元，用于处理含硫气体并回收硫磺，包括液硫池17和依次连接的热反应炉11、一级冷凝器12、一级催化转化器13、二级冷凝器14、二级催化转化器15和三级冷凝器16，所述液硫池17分别与一级冷凝器12、二级冷凝器14和三级冷凝器16相连，用于收集冷却后的液体硫磺；
加氢净化单元，与所述氧化单元连接，用于对氧化单元排出的氧化尾气进行加氢还原并回收加氢还原得到的还原产物中的硫化氢，包括依次连接的加氢反应器21、加氢尾气冷却器22、急冷塔23和吸收塔24；
焚烧单元31，用于焚烧加氢净化单元排出的净化尾气；
吸附单元，用于吸附焚烧得到的含SO 2的烟气中的SO 2，吸附单元中使用的吸附剂为本发明制得的复合材料，包括第一吸附塔41和第二吸附塔42，两个吸附塔可以交替使用以实现连续吸附；
换热单元，包括尾气再热器111和烟气换热器222，所述尾气再热器111设置在氧化单 元和加氢净化单元之间，用于加热氧化单元排出的氧化尾气；所述烟气换热器222设置在焚烧单元和吸附单元之间，用于降低焚烧产生的烟气的温度。
脱硫的步骤如下(具体操作条件如表7所示)：
(a)在氧化单元处理含硫气体并回收硫磺
热反应单元为含85体积％硫化氢的酸性气(CO 2的含量为10体积％、烃的含量为2体积％，NH 3的含量为3体积％)在热反应炉11中部分燃烧转化为二氧化硫：在高温下，硫化氢与二氧化硫发生克劳斯反应生成元素硫和过程气，经一级冷凝器12冷却后元素硫进入液硫池17得到液体硫磺；
过程气依次进入催化反应单元的一级催化转化器13、二级冷凝器14、二级催化转化器15和三级冷凝器16。经Claus催化转化后，元素硫经由二级冷凝器14和三级冷凝器16进入液硫池17；反应后的Claus尾气进入尾气净化单元。
(b)在加氢净化单元对氧化后的尾气进行加氢还原并回收加氢还原得到的还原产物中的硫化氢
Claus尾气经尾气再热器111加热至236℃后进入加氢反应器21，在加氢反应器21内加氢催化剂的作用下，含硫化合物加氢转化为硫化氢，然后经加氢尾气冷却器22、急冷塔23降温，进入具有胺液(KMKTS-15高效脱硫剂，购自淄博凯美可工贸有限公司)的吸收塔24，吸收加氢尾气中的硫化氢，得到净化尾气。
(c)在焚烧单元焚烧加氢还原后的尾气
净化尾气引入焚烧单元(焚烧炉)31中焚烧，产生含SO 2的烟气，烟气引入吸附单元。
(d)在吸附单元使焚烧得到的含SO 2的烟气与吸附剂接触以吸附SO 2
烟气经烟气换热器222换热至145℃后进入处于吸附状态的第一吸附塔41，吸附其中的SO 2后，净化烟气经烟囱排放，净化烟气中SO 2排放控制指标为20mg/m 3。运行初期，净化烟气中未检测到SO 2，运行650h后，烟气中出现SO 2且浓度为1mg/m 3，继续运行至780h后，烟气中SO 2达到8mg/m 3，继续运行至900h后，烟气中SO 2达到20mg/m 3，切除第一吸附塔41，切换第二吸附塔42对焚烧尾气进行吸附。同时对第一吸附塔41通入再生热氮进行热再生，再生产生含SO 2的再生气，再生气引入一级催化转化器13进行再处理。再生时间为100h(相对于20m 3的吸附剂)。待第二吸附塔42排出的净化烟气中SO 2达20mg/m 3时，切换再生后的第一吸附塔41进行吸附。最终通过控制20mg/m 3吸附精度，可以实现硫磺回收装置烟气SO 2排放浓度低于20mg/m 3，满足目前最严格环保法规规定的烟气SO 2降至50mg/m 3以下的要求。而且，再生方式简单，整个处理过程连续清洁。
测试例4
按照测试例3的系统和方法对酸性气进行脱硫，不同的是，将焚烧单元的焚烧炉替换为催化焚烧反应器，再生的方式为水洗再生，如图2所示，水洗再生的方式为：往第一吸附塔41通入水洗水进行吸附剂再生，再生产生再生稀酸，再生稀酸引入热反应炉11进行再处理。再生时间为140h。各个步骤的具体操作条件如表7所示。 表7
Figure PCTCN2020104505-appb-000028
Figure PCTCN2020104505-appb-000029
测试例5
按照测试例3的系统和方法对酸性气进行脱硫，不同的是，吸附单元的温度为180℃，气体体积空速为1000h -1。运行时间为700h时烟气中SO 2达到20mg/m 3。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (29)

  1. 一种分子筛复合物，其特征在于，该分子筛复合物含有铝的氧化物、碱土金属的氧化物和稀土改性分子筛，其中，所述稀土改性分子筛为掺杂有稀土元素的分子筛，所述分子筛复合物中孔径在3nm以下的孔所占的孔体积占总孔体积的百分比≥63.5％；并且该分子筛复合物满足下式I：
    Figure PCTCN2020104505-appb-100001
    式I中：
    W 1表示分子筛复合物中以铝的氧化物计的总铝的重量含量；
    W 2表示分子筛复合物中碱土金属的氧化物的重量含量；
    W 3表示分子筛复合物中以氧化物计的稀土元素的重量含量；
    W 4表示分子筛复合物中以SiO 2计的分子筛的重量含量。
  2. 根据权利要求1所述的分子筛复合物，其中，所述分子筛复合物中孔径在3nm以下的孔所占的孔体积占总孔体积的百分比为63.5-72％。
  3. 根据权利要求1或2所述的分子筛复合物，其中，所述分子筛复合物中孔径小于2nm的孔所占的孔体积占总孔体积的百分比≥35％，孔径为2-3nm的孔所占的孔体积占总孔体积的百分比为20-30％，孔径大于3nm的孔所占的孔体积占总孔体积的百分比为25-40％。
  4. 根据权利要求1-3中任意一项所述的分子筛复合物，其中，所述分子筛复合物中孔径小于2nm的孔所占的孔体积占总孔体积的百分比为39-45.5％。
  5. 根据权利要求1-4中任意一项所述的分子筛复合物，其中，铝的氧化物为Al 2O 3，碱土金属的氧化物为CaO、MgO和BaO中的至少一种，稀土元素为Ce和/或La。
  6. 根据权利要求1-5中任意一项所述的分子筛复合物，其中，所述稀土元素为Ce和La且Ce与La的重量比为1-3。
  7. 根据权利要求1-6中任意一项所述的分子筛复合物，其中，所述稀土改性分子筛为稀土改性Y型分子筛。
  8. 根据权利要求1-7中任意一项所述的分子筛复合物，其中，所述稀土改性分子筛为稀土改性NaY分子筛。
  9. 根据权利要求1-8中任意一项所述的分子筛复合物，其中，所述分子筛复合物的比表面积≥550m 2/g；孔容≥0.25ml/g。
  10. 根据权利要求1-9中任意一项所述的分子筛复合物，其中，所述分子筛复合物的比表面积为550-600m 2/g；孔容为0.25-0.4ml/g。
  11. 根据权利要求1-10中任意一项所述的分子筛复合物，其中，铝的氧化物、碱土金属的氧化物、稀土元素和分子筛之间的重量比为(8-35):(0.5-3):(2.5-10):100。
  12. 根据权利要求1-11中任意一项所述的分子筛复合物，其中，铝的氧化物、碱土金属的氧化物、稀土元素和分子筛之间的重量比为(12-28):(0.6-2.1):(3.7-9.3):100。
  13. 根据权利要求1-12中任意一项所述的分子筛复合物，其中，所述分子筛复合物不含可检测量的Sc、Ti、V、Cr、Mn、Fe、Cu、Zn、W、Ru、Rh、Pd、Ag、Cd、Au、Y或Pt。
  14. 一种复合材料，其特征在于，该复合材料含有权利要求1-13中任意一项所述的分子筛复合物和负载于所述分子筛复合物上的助剂。
  15. 根据权利要求14所述的复合材料，其中，所述助剂为镍的氧化物、钴的氧化物和钼的氧化物中的至少一种。
  16. 根据权利要求15所述的复合材料，其中，镍的氧化物为NiO，钴的氧化物CoO，钼的氧化物为MoO 3。
  17. 根据权利要求14-16中任意一项所述的复合材料，其中，所述复合材料中孔径在3nm以下的孔所占的孔体积占总孔体积的百分比为65-75％。
  18. 根据权利要求14-17中任意一项所述的复合材料，其中，所述复合材料中孔径小于2nm的孔所占的孔体积占总孔体积的百分比≥45％，孔径为2-3nm的孔所占的孔体积占总孔体积的百分比为15-35％，孔径大于3nm的孔所占的孔体积占总孔体积的百分比为20-35％。
  19. 根据权利要求14-18中任意一项所述的复合材料，其中，所述复合材料中孔径小于2nm的孔所占的孔体积占总孔体积的百分比为45-55％。
  20. 根据权利要求14-19中任意一项所述的复合材料，其中，所述复合材料具有基本上如下表1-a所示的X-射线衍射图谱：
    表1-a
    Figure PCTCN2020104505-appb-100002
    Figure PCTCN2020104505-appb-100003
  21. 根据权利要求14-20中任意一项所述的复合材料，其中，所述复合材料的比表面积≥550m 2/g；孔容≥0.25ml/g；饱和硫容≥12％；穿透硫容≥10％。
  22. 根据权利要求14-21中任意一项所述的复合材料，其中，所述复合材料的比表面积为558-580m 2/g；孔容为0.26-0.3ml/g；饱和硫容为12-15％；穿透硫容为10-11％。
  23. 根据权利要求14-22中任意一项所述的复合材料，其中，铝的氧化物、碱土金属的氧化物、稀土元素、助剂和分子筛之间的重量比为(8-35):(0.5-3):(2.5-10):(0.8-4):100。
  24. 根据权利要求14-23中任意一项所述的复合材料，其中，铝的氧化物、碱土金属的氧化物、稀土元素、助剂和分子筛之间的重量比为(12-28):(0.6-2.1):(3.7-9.3):(1.2-3.3):100。
  25. 权利要求1-13中任意一项所述的分子筛复合物或者权利要求14-24中任意一项所述的复合材料在吸附脱硫中的应用。
  26. 一种具有脱硫功能的系统，其特征在于，该系统包括：
    氧化单元，用于处理含硫气体并回收硫磺；
    加氢净化单元，与所述氧化单元连接，用于对氧化单元排出的氧化尾气进行加氢还原并回收加氢还原得到的还原产物中的硫化氢；
    焚烧单元，用于焚烧加氢净化单元排出的净化尾气；
    吸附单元，用于吸附焚烧得到的含SO 2的烟气中的SO 2，吸附单元中使用的吸附剂为权利要求14-24中任意一项所述的复合材料；
  27. 根据权利要求26所述的系统，其中，所述吸附单元还包括再生物的入口和出口，用于将再生物引入吸附单元对吸附剂进行再生；且所述吸附单元进一步与氧化单元相连，使得再生得到的含SO 2的再生气返回氧化单元进行再处理。
  28. 一种脱硫的方法，其特征在于，该方法包括：
    (a)氧化待处理的含硫气体并回收硫磺；
    (b)对氧化后的尾气进行加氢还原并回收加氢还原得到的还原产物中的硫化氢；
    (c)焚烧加氢还原后的尾气；
    (d)使焚烧得到的含SO 2的烟气与吸附剂接触以吸附SO 2，所述吸附剂为权利要求14-24中任意一项所述的复合材料。
  29. 根据权利要求28所述的方法，其中，步骤(d)中，所述接触的条件包括：温度为100-150℃，气体体积空速为1500-2000h -1；
    和/或，所述方法还包括对吸附剂进行再生，并将再生得到的含SO 2的再生气返回步骤(a)进行再处理；
    和/或，所述方法在权利要求26或27所述的系统中的实施。
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