WO2018152829A1 - Cu-SAPO分子筛、合成方法及其催化应用 - Google Patents

Cu-SAPO分子筛、合成方法及其催化应用 Download PDF

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WO2018152829A1
WO2018152829A1 PCT/CN2017/074985 CN2017074985W WO2018152829A1 WO 2018152829 A1 WO2018152829 A1 WO 2018152829A1 CN 2017074985 W CN2017074985 W CN 2017074985W WO 2018152829 A1 WO2018152829 A1 WO 2018152829A1
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molecular sieve
source
sample
per mole
moles
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田鹏
向骁
刘中民
曹磊
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Dalian Institute of Chemical Physics of CAS
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Priority to PCT/CN2017/074985 priority Critical patent/WO2018152829A1/zh
Priority to US16/488,732 priority patent/US20210130179A1/en
Priority to EP17897284.0A priority patent/EP3586960B1/en
Priority to JP2019543950A priority patent/JP6990712B2/ja
Priority to RU2019130327A priority patent/RU2730479C1/ru
Priority to AU2017400922A priority patent/AU2017400922B2/en
Priority to MYPI2019004880A priority patent/MY192640A/en
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/001—Calcining
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F01N3/2066—Selective catalytic reduction [SCR]
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
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    • B01D2251/2062—Ammonia
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/05—Nuclear magnetic resonance [NMR]
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
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    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
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    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/14—Nitrogen oxides

Definitions

  • the invention relates to a novel copper-containing SAPO molecular sieve, a synthesis method and the application thereof in denitration reaction.
  • Nitrogen oxide pollution mainly comes from the emission of mobile source vehicle exhaust gas and the emission of fixed source factory exhaust gas, NOx.
  • the treatment of pollution is carried out by selective catalytic reduction of NH 3 , urea or hydrocarbon as a reducing agent, which is converted into harmless nitrogen.
  • the traditional denitration catalyst is mainly V-Ti-W system.
  • the exhaust gas emission temperature of the lean-burn exhaust gas is lowered, and the narrower temperature range of the catalyst of the V-Ti-W system cannot meet the requirements. And its potential for environmental pollution limits its application.
  • the copper-based catalyst and the iron-based catalyst are two representative systems, and the copper-based catalyst exhibits excellent low-temperature activity, but an excessively high load causes a severe NH 3 oxidation reaction in the high temperature section.
  • Iron-based catalysts have excellent high temperature activity, but their lower conversion rate in the low temperature range limits their use in certain fields.
  • Small pore molecular sieves such as SSZ-13 and SAPO-34 can effectively improve the high temperature hydrothermal stability of the catalyst, and when loaded with copper as the active metal, it has high NO conversion activity in a wide temperature range. High N 2 selectivity. Although it has problems such as sensitivity to sulfur, this problem has gradually been resolved with the improvement of oil quality.
  • the invention provides a one-step synthesis method of Cu-SAPO molecular sieve catalyst with controlled Cu content, and exhibits excellent deNOx catalytic activity, and has potential application value.
  • the novel molecular sieve synthesized by the invention exhibits the characteristics of coexistence of broad peaks and peaks, and its XRD diffraction spectrum and literature (Microporous and Mesoporous Materials, 30 (1999) 335-346; official website of the International Molecular Sieve Association http://www .iza-structure.org/databases/Catalog/ABC_6.pdf )
  • the spectra of silicoalulites with GME/CHA symbiotic structure are similar.
  • We analyzed this type of molecular sieve as a novel SAPO molecular sieve with a GME/CHA symbiotic structure.
  • a Cu-SAPO molecular sieve having a CHA and a GME symbiotic crystal phase, characterized in that the X-ray diffraction pattern of the molecular sieve contains at least the following diffraction peaks:
  • m can be from 0.02 to 0.15; n can be from 0.01 to 0.09; x can be from 0.05 to 0.28; y can be from 0.40 to 0.50; z can be from 0.30 to 0.50; and w can be from 0.005 to 0.100.
  • Another object of the present invention is to provide a method for synthesizing the above Cu-SAPO molecular sieve, which comprises the following steps:
  • SiO 2 /Al 2 O 3 0.05 to 2.0;
  • R1 is diisopropanolamine (DIPA) or diethanolamine (DEOA);
  • R2 is trimethylamine (TMA), benzyltrimethylammonium chloride (BTACl), benzyltrimethylammonium hydroxide (BTAOH) Any one or a mixture of any of several.
  • the specific batching sequence can be as follows: the copper source is first dissolved in water, then R1 and R2 are added, and stirred at room temperature for 0.5-5 h. Subsequently, an aluminum source, a silicon source and a phosphorus source were sequentially added to the mixed solution, and the mixed gel was stirred at room temperature for 1-5 h.
  • step b) The initial gel mixture obtained in the step a) is placed in a high pressure synthesis reactor, sealed, heated to 160 to 220 ° C, and crystallized for 5 to 72 hours.
  • the silicon source in step a) is selected from one or more of silica sol, active silica, orthosilicate, metakaolin;
  • the aluminum source is selected from the group consisting of aluminum salt, activated alumina, and thin One or more of diaspore, alkoxy aluminum, metakaolin;
  • the phosphorus source is selected from one or more of orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphide, and phosphorus oxide.
  • the copper source is one or more selected from the group consisting of Cu(OAc) 2 , CuSO 4 , Cu(NO 3 ) 2 , CuCl 2 and the like.
  • step b) The crystallization process in step b) is carried out either statically or dynamically.
  • said step a) initially in the gel mixture P 2 O 5 /Al 2 O 3 0.8 to 1.5.
  • the organic templating agent benzyltrimethylammonium chloride (BTACl) and benzyltrimethylammonium hydroxide (BTAOH) in R2 are decomposed in the molecular sieve synthesis to form trimethylamine and enter the pore cage of the molecular sieve.
  • the R1/R2 molar ratio preferably ranges from 16 to 60; and when R1 is diisopropanolamine, the preferred crystallization temperature is from 195 to 220 °C.
  • a further object of the present application is to provide a catalyst for removing NO x selective reduction reaction, it was 550 ⁇ 700 °C was air calcined in the above-described molecular sieves and / or molecular sieve synthesized according to the method described above.
  • a novel Cu-SAPO molecular sieve is provided.
  • the prepared molecular sieve can be used as a catalyst for catalytic removal of nitrogen oxides and exhibits good catalytic performance.
  • Figure 1 is an XRD pattern of the synthesized product in Example 1.
  • Example 2 is a scanning electron micrograph (SEM) of the synthesized product of Example 1.
  • Figure 4 is a comparison of NH 3 -SCR reaction evaluation results for catalysts with different copper contents (Examples 11-13)
  • Figure 5 is a comparison of the evaluation results of NH 3 -SCR reaction before and after high temperature hydrothermal treatment of the sample of Example 1 (Example 11 and Example 14)
  • Figure 6 is an XRD result of a sample corresponding to Comparative Example 3-8.
  • test conditions of this application are as follows:
  • the elemental composition was determined using a Philips Magix 2424X ray fluorescence analyzer (XRF).
  • the FT-IR is collected using the German BRUKER TENSOR 27 instrument.
  • the specific surface area and pore size distribution of the samples were determined using a Micromeritics ASAP Model 2020 physical adsorber. Before the analysis, the sample was preheated at 350 ° C for 6 h, and the free volume of the sample tube was measured with He as the medium. When the sample was analyzed, the adsorption and desorption measurements were carried out at a liquid nitrogen temperature (77 K) using nitrogen as an adsorption gas. The specific surface area of the material was determined using the BET formula; the total pore volume of the material was calculated using the adsorption amount of N 2 at a relative pressure (P/P 0 ) of 0.99. The micropore surface area and micropore volume were calculated by the t-plot method. When calculated, the cross-sectional area of the N 2 molecule was taken to be 0.162 nm 2 .
  • the SEM morphology analysis was performed using a Hitachi (SU8020) type scanning electron microscope.
  • Carbon nuclear magnetic resonance ( 13 C MAS NMR) analysis was performed using a Varian Infinity plus 400 WB solid-state nuclear magnetic spectrum analyzer with a BBO MAS probe operating at a magnetic field strength of 9.4T.
  • the CHN elemental analysis was performed using a Vario EL Cube elemental analyzer made in Germany.
  • the molar ratio of each raw material and the crystallization conditions are shown in Table 2.
  • the specific batching process is as follows: the copper source is first dissolved in water, then R1 and R2 are added, and stirred at room temperature for 2 h. Subsequently, an aluminum source, a silicon source and a phosphorus source were sequentially added to the mixed solution, and the mixed gel was stirred at room temperature for 5 hours to form a gel, and the gel was transferred to a stainless steel reaction vessel. After the reactor was placed in an oven, it was heated at a rate of 2 ° C/min to 200 ° C for crystallization for 36 h.
  • the solid product was centrifuged, washed, and dried in air at 100 ° C to obtain a sample of the molecular sieve raw powder.
  • the sample was subjected to XRD analysis, and the peak shape exhibited characteristics of broad peaks and peaks.
  • the XRD diffraction pattern is shown in Fig. 1, and the XRD diffraction data is shown in Table 3.
  • the specific surface area and pore volume were measured.
  • the sample had a high BET specific surface area of 602 m 2 g -1 and a large pore volume of 0.27 cm 3 g -1 , which was calculated according to the t-plot method.
  • the specific pore surface area and micropore volume were 533 m 2 g -1 and 0.26 cm 3 g -1 , respectively .
  • the scanning electron micrograph of the obtained sample is shown in Fig. 2. It can be seen that the morphology of the obtained sample is a layered stacked disc having a particle size ranging from 3 to 5 ⁇ m.
  • Example 2 The specific proportion of ingredients and crystallization conditions are shown in Table 2, and the specific batching process is the same as in Example 1.
  • the synthesized samples were subjected to XRD analysis.
  • the results of XRD data of Examples 4 and 9 were similar to those of Table 3.
  • the results of XRD data of Examples 5 and 6 were similar to those of Table 4, and the results of XRD data of Examples 7 and 8 were close to Table 5.
  • CHA crystal phase in the silicon-phosphorus aluminum molecular sieve provided in Examples 1-9 is obvious by comparison with the diffraction spectrum of the different proportions of GME/CHA symbiotic silicoaluminosilicate crystal phase given on the official website of the International Molecular Sieve Association. Higher than the GME crystal phase.
  • the CHN elemental analysis of the original powder samples of Examples 1-9 was carried out by XRF analysis of the bulk elemental composition of the molecular sieve product.
  • the composition of the molecular sieve raw powder obtained by comprehensive CHN elemental analysis, XRF and 13 C MAS NMR analysis is shown in Table 6.
  • Example Sample raw powder composition 1 0.038Cu0.07DEOA0.02TMA(Si 0.203 Al 0.470 P 0.327 )O 2 2 0.008Cu0.04DEOA0.01TMA(Si 0.032 Al 0.490 P 0.478 )O 2 3 0.029Cu0.081DIPA0.058TMA (Si 0.205 Al 0.488 P 0.307 )O 2 4 0.040Cu0.13DEOA0.048TMA(Si 0.165 Al 0.488 P 0.347 )O 2 5 0.018Cu0.07DEOA0.02TMA(Si 0.072 Al 0.470 P 0.458 )O 2 6 0.035Cu0.11DEOA0.034TMA(Si 0.155 Al 0.488 P 0.357 )O 2 7 0.020Cu0.12DEOA0.038TMA(Si 0.100 Al 0.488 P 0.412 )O 2
  • the raw powder samples of Examples 1-9 were separately mixed with potassium bromide and ground and pressed, and subjected to FT-IR characterization. Both of them showed a characteristic vibration absorption peak attributed to the double six-membered ring at 637 cm -1 . There is a double six-membered ring in the sample.
  • Samples obtained in Example 1 was calcined temperature 650 °C 2h, after removal of the template agent for selective reduction of NH 3 reacts with NO x removal catalyst properties were characterized.
  • the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
  • the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 as a balance gas, and a gas flow rate of 300 mL/min.
  • the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The results are shown in Figures 3 and 4. It can be seen that the conversion of NO at the reaction temperature is 77% at 150 ° C, and the conversion of NO is greater than 90% over a wide temperature range of 180 - 450 ° C. Similarly, the samples obtained in Example 2-8 after the same as in Example 1, treated sample also showed a better removal of NO x selective reduction of catalytic performance.
  • Example 3 The sample obtained in Example 3 at 650 °C calcination temperature 2h, after removal of the template agent for selective reduction of NH2 3 reacts with NO x removal catalyst properties were characterized.
  • the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
  • the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 as a balance gas, and a gas flow rate of 300 mL/min.
  • the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The results are shown in Figure 4.
  • Example 8 The sample obtained in Example 8 at 650 °C calcination temperature 2h, after removal of the template agent for selective reduction of NH 3 reacts with NO x removal catalyst properties were characterized.
  • the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
  • the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 as a balance gas, and a gas flow rate of 300 mL/min.
  • the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The reaction results are shown in Figure 4.
  • Example 1 The sample obtained in Example 1 was calcined at 650 ° C for 2 h, and after removing the templating agent, hydrothermal aging treatment was carried out at 800 ° C, the water vapor content was 100%, the treatment time was 24 h, and after the treatment, it was dried at 100 ° C.
  • the relative crystallinity of the sample was determined by XRD method, and the crystallinity of the sample was 95% of the sample of Example 1, indicating that the sample prepared in Example 1 has high hydrothermal stability and can be well maintained after water treatment. Its structural integrity.
  • Example 9 10 g of the sample molecular sieve raw powder obtained in Example 9 was used as a precursor, and was heated at a rate of 2 ° C/min to a constant temperature of 600 ° C for 4 hours to remove the organic templating agent and water contained therein.
  • the calcined sample was placed in a 3.66 mol/L ammonium nitrate aqueous solution at a solid-liquid ratio (mass ratio) of 1:10, stirred for five minutes, and then heated to 80 ° C for ion exchange for 2 hours. It was then separated by centrifugation and washed three times with deionized water and dried at 80 ° C to obtain a NH 4 + type molecular sieve.
  • Example 9 Samples of the microporous surface area and pore volume were 559m 2 g -1 and 0.28cm 3 g -1, porous Cu-9 / T samples of specific surface area and pore volume of 520m 2 g -1, respectively, And 0.25cm 3 g -1 . These results show that the catalyst prepared according to the method of Example 1 can better maintain the regularity of the sample skeleton structure.
  • the sample obtained in Comparative Example 1 was calcined at a high temperature of 650 ° C for 2 h, and used as a catalyst for selective reduction of NOx by NH 3 .
  • the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
  • the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 was a balance gas, and the total gas flow rate was 300 mL/min.
  • the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The specific results are shown in Figure 3.
  • the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 1, except that the diethanolamine in the raw material was replaced with triethylamine.
  • the synthetic sample was SAPO-34 molecular sieve, and the XRD analysis results are shown in Fig. 6.
  • the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 2 except that the benzyltrimethylammonium hydroxide in the raw material was replaced with 1,6-hexanediamine.
  • the synthesized sample is a layered phase.
  • the XRD results are shown in Figure 6.
  • the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 3, except that the addition of trimethylamine in the raw materials was omitted.
  • the synthetic sample was a physical mixture of SAPO-34 and SAPO-5, and the XRD results are shown in Figure 6.
  • the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 4, except that the diethanolamine in the raw material was replaced with diethylamine.
  • the synthesized sample was a physical mixture of a small amount of SAPO-34 DNL-6 (SAPO molecular sieve with RHO structure), and the XRD results are shown in Fig. 6.
  • the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 5 except that the trimethylamine in the raw material was replaced with triethanolamine.
  • the synthetic sample was a physical mixture of SAPO-5 and SAPO-34, and the XRD results are shown in Figure 6.
  • the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 5, except that the addition of trimethylamine in the raw materials was omitted.
  • the synthesized sample was amorphous, and the XRD analysis results are shown in Fig. 6.

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Abstract

一种具有CHA和GME共生晶相的Cu-SAPO分子筛及其合成方法和在脱硝反应中的应用。Cu-SAPO分子筛的XRD衍射谱图呈现宽峰和尖峰共存的特征，无机骨架具有如下的化学组成：wCu-(Si xAl yP z)O 2，其中：x、y、z分别表示Si、Al、P的摩尔分数，其范围分别是x＝0.01～0.28，y＝0.35～0.55，z＝0.28～0.50，且x+y+z＝1，w为每摩尔(Si xAl yP z)O 2对应的Cu的摩尔数，w＝0.001～0.124。该合成的分子筛可用作NO x选择还原脱除反应的催化剂。

Description

Cu-SAPO分子筛、合成方法及其催化应用 技术领域
本发明涉及一种新型的含铜SAPO分子筛、合成方法及其在脱硝反应中的应用。
背景技术
NOx作为主要大气污染物之一，能引起酸雨，光化学烟雾等诸多环境问题，且对人体健康构成严重危害，氮氧化物污染主要来源于移动源汽车尾气的排放和固定源工厂废气的排放，NOx污染的处理方法是以NH3，尿素或者碳氢化合物为还原剂进行选择催化还原反应，将其转化为无害的氮气。传统的脱硝催化剂主要是V-Ti-W体系，但是随着发动机技术中稀燃技术的广泛采用，稀燃尾气排放温度降低，V-Ti-W体系的催化剂较窄温度适用范围不能满足要求，而且其潜在的对环境造成污染的可能性也限制了其应用。分子筛催化体系逐渐成为目前的研究热点。在分子筛体系的催化剂中，铜系催化剂和铁系催化剂是两类具有代表性的体系，铜系催化剂表现出优良的低温活性，但是过高的负载量会造成高温段严重的NH3氧化反应。铁基催化剂有着优良的高温活性，但其在低温段较低的转化率限制了其在某些领域的应用。
1986年，Iwamoto等人首次报道了Cu2+交换的ZSM-5有催化NO直接分解为N2和O2的能力，在之后的研究中，由于研究者较为关注以碳氢化合物为还原剂的SCR反应，Fe-ZSM-5逐渐成为下一个研究热点。与氧化物催化剂相比，分子筛体系催化剂的优点是具有较宽的反应温度窗口，良好的热稳定性，且在高温下抗硫中毒能力较强，但是，它们也存在一些问题，比如，高温水热稳定性较差，低温抗硫性能较差等。
小孔分子筛如SSZ-13和SAPO-34作为载体材料，能够有效提升催化剂的高温水热稳定性，且负载铜作为活性金属的时候，其在较宽的温度范围内有着高的NO转化活性和高的N2选择性。虽然其存在 着对硫敏感等问题，但是这一问题随着油品质量的提升，也逐步得到解决。
通常SAPO分子筛的合成需要有机胺/铵作为结构导向剂，通过水热或溶剂热的方法合成得到。合成方法的创新以及模板剂的选择对于产物结构和性能的控制具有至关重要的影响。以铜胺络合物为模板剂可以一步法合成Cu-SAPO-18和Cu-SAPO-34。这种一步法合成的Cu-SAPO催化剂简化了催化剂的制备过程，具有重要的意义。且这种一步法合成的Cu-SAPO型催化剂表现出了优异的NH3-SCR催化活性，以及组成的可调变性，具有一定的工业应用的前景。
本发明提供了一种Cu含量可控的一步法合成Cu-SAPO分子筛催化剂的方法，且表现出优良的deNOx催化活性，具有潜在的应用价值。
发明内容
本发明的目的在于提供一种具有GME和CHA共晶结构的Cu-SAPO分子筛。
本发明所合成的新型分子筛，呈现宽峰和尖峰共存的特征，其XRD衍射谱图与文献中(Microporous and Mesoporous Materials,30(1999)335–346；国际分子筛协会的官方网站http://www.iza-structure.org/databases/Catalog/ABC_6.pdf)具有GME/CHA共生结构的硅铝沸石的谱图具有相似性。我们分析该类分子筛是具有GME/CHA共生结构的新型SAPO分子筛。
根据本发明的实施方案，提供一种具有CHA和GME共生晶相的Cu-SAPO分子筛，其特征在于，所述分子筛的X射线衍射图谱至少含有以下衍射峰：
表1
Figure PCTCN2017074985-appb-000001
Figure PCTCN2017074985-appb-000002
分子筛的无机骨架具有如下的化学组成：wCu-(SixAlyPz)O2，其中：x、y、z分别表示Si、Al、P的摩尔分数，其范围分别是x＝0.01～0.28，y＝0.35～0.55，z＝0.28～0.50，且x+y+z＝1，w为每摩尔(SixAlyPz)O2对应的Cu的摩尔数，w＝0.001～0.124。
分子筛包含模板剂的无水化学组成可表示为：wCu mR1 nR3(SixAlyPz)O2，其中：R1为二异丙醇胺或二乙醇胺，R3为三甲胺；m为每摩尔(SixAlyPz)O2中R1模板剂的摩尔数，n为每摩尔(SixAlyPz)O2中R3模板剂的摩尔数，m＝0.01～0.20，n＝0.01～0.10；x、y、z分别表示Si、Al、P的摩尔分数，其范围分别是x＝0.01～0.28，y＝0.35～0.55，z＝0.28～0.50，且x+y+z＝1；w为每摩尔(SixAlyPz)O2对应的Cu的摩尔数，w＝0.001～0.124。在某些实施方案中，m可以为0.02～0.15；n可以为0.01～0.09；x可以为0.05～0.28；y可以为0.40～0.50；z可以为0.30～0.50；w可以为0.005～0.100。
本发明的又一目的在于提供上述Cu-SAPO分子筛的合成方法，其特征在于，包括如下步骤：
a)将铜源，去离子水、模板剂R1和R2，硅源、铝源和磷源按比例混合，得到具有如下摩尔配比的初始凝胶混合物：
Cu/Al2O3＝0.01～0.25；
SiO2/Al2O3＝0.05～2.0；
P2O5/Al2O3＝0.5～1.5；
H2O/Al2O3＝8～40；
R1/Al2O3＝5～20；
R2/Al2O3＝0.1～1.5；
其中，R1为二异丙醇胺(DIPA)或二乙醇胺(DEOA)；R2为三甲胺(TMA)、苄基三甲基氯化铵(BTACl)、苄基三甲基氢氧化铵(BTAOH)中的任意一种或任意几种的混合物。
具体配料顺序可以如下：铜源首先与水混合溶解，然后再加入R1和R2，并在室温搅拌0.5-5h。随后，依次向混合液中加入铝源，硅源和磷源，并将混合凝胶在室温搅拌1-5h。
b)将步骤a)所得初始凝胶混合物装入高压合成釜，密闭，升温到160～220℃，晶化5～72小时。
c)待晶化完成后，固体产物经分离、洗涤、干燥后，即得所述的分子筛。
其中，步骤a)中所述硅源选自硅溶胶、活性二氧化硅、正硅酸酯、偏高岭土中的一种或几种；所述铝源选自铝盐、活性氧化铝、拟薄水铝石、烷氧基铝、偏高岭土中的一种或几种；所述磷源选自正磷酸、磷酸氢铵、磷酸二氢铵、有机磷化物、磷氧化物中的一种或几种；所述铜源选自Cu(OAc)2,CuSO4,Cu(NO3)2,CuCl2等含铜的无机盐中的一种或几种。
所述步骤b)中的晶化过程在静态或动态下进行。
优选地，所述步骤a)初始凝胶混合物中SiO2/Al2O3＝0.20～1.8。
优选地，所述步骤a)初始凝胶混合物中P2O5/Al2O3＝0.8～1.5。
优选地，所述步骤a)初始凝胶混合物中R1/Al2O3＝5.0～10。
优选地，所述步骤a)初始凝胶混合物中R2/Al2O3＝0.25～1.0。
R2中的有机模板剂苄基三甲基氯化铵(BTACl)和苄基三甲基氢氧化铵(BTAOH)在分子筛合成中会发生分解，生成三甲胺，进入分子筛的孔笼内。
在上述合成分子筛的方法中，当R1为二乙醇胺时，R1/R2摩尔比例优选范围为16-60；当R1为二异丙醇胺时，优选的晶化温度为195-220℃。
本申请的又一目的在于提供一种NOx选择还原脱除反应的催化剂，它是通过上述的分子筛和/或根据上述方法合成的分子筛经550～700℃空气中焙烧得到。
本发明能产生的有益效果包括：
(1)提供一种新型Cu-SAPO分子筛。
(2)所制备的分子筛可作为催化剂用氮氧化物的催化脱除反应，并表现出良好的催化性能。
附图说明
图1是实施例1中合成产物的XRD图谱
图2是实施例1合成产物的扫描电镜图(SEM)
图3是实施例11和对比例2的NH3-SCR反应评价结果
图4是不同铜含量(实施例11-13)催化剂的NH3-SCR反应评价结果对比
图5是实施例1样品高温水热处理前后(实施例11及实施例14)NH3-SCR反应评价结果对比
图6是对比例3-8对应样品的XRD结果
具体实施方式
下面结合实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。未做特殊说明的情况下，本申请所使用原料，均通过商业途径购买，不经特殊处理直接使用。
未做特殊说明的情况下，本申请的测试条件如下：
元素组成采用Philips公司的Magix 2424X型射线荧光分析仪(XRF)测定。
FT-IR采用德国BRUKER TENSOR 27仪器进行采集。
X射线粉末衍射物相分析(XRD)采用荷兰帕纳科(PANalytical)公司的X’Pert PRO X射线衍射仪，Cu靶，Kα辐射源(λ＝0.15418nm)，电压40KV，电流40mA。
采用美国Micromeritics公司ASAP 2020型物理吸附仪测定样品的比表面积和孔径分布。分析前，样品在350℃下抽真空加热预处理6h，以He为介质测量样品管自由体积。分析样品时，以氮气为吸附气体，在液氮温度(77K)下进行物理吸附和脱附测定。采用BET 公式确定材料的比表面积；使用相对压力(P/P0)为0.99时的N2的吸附量计算材料的总孔容。用t-plot方法计算微孔表面积和微孔孔容。计算时，N2分子横截面积取0.162nm2。
SEM形貌分析采用Hitachi(SU8020)型扫描电子显微镜。
碳核磁共振(13C MAS NMR)分析采用美国Varian公司的Infinity plus 400WB固体核磁波谱分析仪，用BBO MAS探针，操作磁场强度为9.4T。
CHN元素分析采用德国制造的Vario EL Cube元素分析仪。
下面通过实施例详述本发明，但本发明并不局限于这些实施例。
实施例1
各原料摩尔比例和晶化条件见表2。具体配料过程如下：铜源首先与水混合溶解，然后再加入R1和R2，并在室温搅拌2h。随后，依次向混合液中加入铝源，硅源和磷源，并将混合凝胶在室温搅拌5h，制成凝胶，将凝胶转移到不锈钢反应釜中。反应釜放入烘箱后，以2℃/min速率升温到200℃转动条件下晶化36h。晶化结束后，将固体产物离心，洗涤，在100℃空气中烘干后，得到所述分子筛原粉样品。样品做XRD分析，峰形呈现宽峰和尖峰共存的特征，XRD衍射图见图1，XRD衍射数据见表3。将样品焙烧脱除模板剂后，测其比表面积及孔容，样品具有高的BET比表面积602m2g-1，及大的孔体积0.27cm3g-1，其中按照t-plot方法计算得到的微孔比表面积和微孔容积分别为533m2g-1和0.26cm3g-1。
所得样品的扫描电镜照片如图2所示，可以看出，所得样品的形貌为层状堆积的圆片状，粒径范围为3～5μm。
表2：分子筛合成配料及晶化条件表
Figure PCTCN2017074985-appb-000003
Figure PCTCN2017074985-appb-000004
表3实施例1样品的XRD结果
Figure PCTCN2017074985-appb-000005
Figure PCTCN2017074985-appb-000006
实施例2
具体配料比例和晶化条件见表2，具体配料过程同实施例1。
合成样品做XRD分析，代表性的数据结果见表4。
扫描电镜照片显示，所得样品的形貌与实施例1样品类似。
表4实施例2样品的XRD结果
Figure PCTCN2017074985-appb-000007
实施例3
具体配料比例和晶化条件见表2，具体配料过程同实施例1。
合成样品做XRD分析，代表性的数据结果见表5。
扫描电镜照片显示，所得样品的形貌与实施例1样品类似。
表5实施例3样品的XRD结果
Figure PCTCN2017074985-appb-000008
Figure PCTCN2017074985-appb-000009
实施例4-9
具体配料比例和晶化条件见表2，具体配料过程同实施例1。合成样品做XRD分析，实施例4、9的XRD数据结果与表3接近，实施例5、6的XRD数据结果与表4接近，实施例7、8的XRD数据结果与表5接近。
通过与国际分子筛协会官方网站上给出的不同比例GME/CHA共生硅铝沸石晶相的衍射谱图比对，实施例1-9中所提供的硅磷铝分子筛中CHA晶相的含量要明显高于GME晶相。
实施例10
对实施例1-9粉样品进行13C MAS NMR分析，通过与二异丙醇胺、二乙醇胺和三甲胺的13C MAS NMR标准谱图对照，发现以二异丙醇胺为溶剂合成的样品同时具有二异丙醇胺和三甲胺的共振峰，以二乙醇胺为溶剂合成的样品同时具有二乙醇胺和三甲胺的共振峰。依据两种物质特有不重合的NMR峰进行定量分析，确定两者的比例。
采用XRF分析分子筛产品体相元素组成，对实施例1-9原粉样品进行CHN元素分析。综合CHN元素分析、XRF和13C MAS NMR分析结果，得到分子筛原粉的组成见表6。
表6实施例1-9的原粉样品的组成
实施例 样品原粉组成
1 0.038Cu0.07DEOA0.02TMA(Si0.203Al0.470P0.327)O2
2 0.008Cu0.04DEOA0.01TMA(Si0.032Al0.490P0.478)O2
3 0.029Cu0.081DIPA0.058TMA(Si0.205Al0.488P0.307)O2
4 0.040Cu0.13DEOA0.048TMA(Si0.165Al0.488P0.347)O2
5 0.018Cu0.07DEOA0.02TMA(Si0.072Al0.470P0.458)O2
6 0.035Cu0.11DEOA0.034TMA(Si0.155Al0.488P0.357)O2
7 0.020Cu0.12DEOA0.038TMA(Si0.100Al0.488P0.412)O2
8 0.09Cu0.07DEOA0.02TMA(Si0.203Al0.470P0.327)O2
9 0.07DEOA0.02TMA(Si0.203Al0.470P0.327)O2
将实施例1-9的原粉样品分别与溴化钾混合研磨压片，进行FT-IR表征，它们均在637cm-1处出现非常明显的归属于双六元环的特征振动吸收峰，显示样品中存在双六元环。
实施例11
将实施例1得到的样品于650℃高温焙烧2h，除去模板剂后，用于NH3选择性还原脱除NOx反应的催化性能进行表征。具体实验过程和条件如下：焙烧后样品压片筛分，称取0.1g 60到80目样品与0.4g石英砂(60到80目)混合，装入固定床反应器。于600℃下通氮气活化40min，然后降温至120℃开始反应，并程序升温到550℃。反应原料气为：NO：500ppm，NH3：500ppm，O2：5％，H2O：5％，N2作为平衡气，气体流速300mL/min。反应尾气采用Bruker公司的Tensor 27型仪器，进行在线FTIR分析，结果见图3和图4。可以看到，反应在150℃时NO的转化率达77％，在180–450℃较宽的温度范围内，NO的转化率大于90％。类似地，实施例2-8得到的样品经过与实施例1样品相同的处理后也展现了较好的选择性还原脱除NOx催化性能。
实施例12
将实施例3得到的样品于650℃高温焙烧2h，除去模板剂后，用于NH3选择性还原脱除NOx反应的催化性能进行表征。具体实验过程和条件如下：焙烧后样品压片筛分，称取0.1g 60到80目样品与0.4g石英砂(60到80目)混合，装入固定床反应器。于600℃下通氮气活化40min，然后降温至120℃开始反应，并程序升温到550℃。反应原料气为：NO：500ppm，NH3：500ppm，O2：5％，H2O：5％，N2作为平衡气，气体流速300mL/min。反应尾气采用Bruker公司的Tensor 27型仪器，进行在线FTIR分析,反应结果见图4。
实施例13
将实施例8得到的样品于650℃高温焙烧2h，除去模板剂后，用于NH3选择性还原脱除NOx反应的催化性能进行表征。具体实验过程和条件如下：焙烧后样品压片筛分，称取0.1g 60到80目样品与0.4g石英砂(60到80目)混合，装入固定床反应器。于600℃下通氮气活化40min，然后降温至120℃开始反应，并程序升温到550℃。反应原料气为：NO：500ppm，NH3：500ppm，O2：5％，H2O：5％，N2作为平衡气，气体流速300mL/min。反应尾气采用Bruker公司的Tensor 27型仪器，进行在线FTIR分析。反应结果见图4。
实施例14
将实施例1得到的样品于650℃高温焙烧2h，除去模板剂后，于800℃进行水热老化处理，水蒸气含量为100％，处理时间为24h,处理结束后，于100℃烘干。
用XRD方法测定样品的相对结晶度，样品的结晶度为实施例1样品的95％，表明实施例1所制备的样品有着较高的水热稳定性，在水处理后，能够较好地保持其结构的完整性。
用于NH3选择性还原脱除NOx反应的催化性能进行表征。具体实验过程和条件如下：样品压片筛分，称取0.1g 60到80目样品与0.4g石英砂(60到80目)混合，装入固定床反应器。于600℃下通氮气活化40min，然后降温至120℃开始反应，并程序升温到550℃。反应原料气为：NO：500ppm，NH3：500ppm，O2：5％，H2O：5％，N2作为平衡气，气体流速300mL/min。反应尾气采用Bruker公司的Tensor 27型仪器，进行在线FTIR分析。反应结果见图5。
对比例1：
以10g实施例9得到的样品分子筛原粉为前躯体，以2℃/min的速度升温到600℃恒温焙烧4h，除去其中所含的有机模板剂和水。
按照1:10的固液比(质量比)将焙烧过的样品投入3.66mol/L的硝酸铵水溶液，搅拌五分钟后，升温到80℃离子交换2h。然后离 心分离，并用去离子水洗涤三次，80℃烘干，即得NH4 +型分子筛。
将7g NH4 +型分子筛按照1:25的固液比投入0.03mol/L的Cu(CH3COO)2·H2O溶液，搅拌5分钟，升温到50℃离子交换4h。然后离心分离，并用去离子水洗涤3次，80℃烘干，所得样品记为Cu-9/T。XRF元素分析结果显示，产品的氧化铜含量3.2％，与实施例1接近。采用N2物理吸附测定焙烧型实施例9样品及Cu-9/T样品的比表面积及孔容，按照t-plot方法计算得到的微孔比表面积和微孔容积。实施例9样品的微孔比表面积和微孔容积分别为559m2g-1和0.28cm3g-1，Cu-9/T样品的微孔比表面积和微孔容积分别为520m2g-1和0.25cm3g-1。这些结果显示按照实施例1方法制备的催化剂能更好地保持样品骨架结构的规整性。
对比例2
将对比例1得到的样品于650℃高温焙烧2h，用作NH3选择性还原脱除NOx反应的催化剂。具体实验过程和条件如下：焙烧后样品压片筛分，称取0.1g 60到80目样品与0.4g石英砂(60到80目)混合，装入固定床反应器。于600℃下通氮气活化40min，然后降温至120℃开始反应，并程序升温到550℃。反应原料气为：NO：500ppm，NH3：500ppm，O2：5％，H2O：5％，N2为平衡气，气体总流速300mL/min。反应的总空速GHSV＝180000h-1。反应尾气采用Bruker公司的Tensor27型仪器，进行在线FTIR分析。具体结果见图3。
对比例3
具体配料摩尔比例、原料和晶化条件同实施例1，不同的是将原料中的二乙醇胺用三乙胺替代。合成样品为SAPO-34分子筛，XRD分析结果见图6。
对比例4
具体配料摩尔比例、原料和晶化条件同实施例2，不同的是将原料中的苄基三甲基氢氧化铵用1,6-己二胺替代。合成样品为为层状相， XRD结果见图6。
对比例5
具体配料摩尔比例、原料和晶化条件同实施例3，不同的是省去原料中的三甲胺的添加。合成样品为SAPO-34和SAPO-5的物理混合物，XRD结果见图6。
对比例6
具体配料摩尔比例、原料和晶化条件同实施例4，不同的是将原料中的二乙醇胺用二乙胺替代。合成样品为少量SAPO-34的DNL-6(具有RHO结构的SAPO分子筛)的物理混合物，XRD结果见图6。
对比例7
具体配料摩尔比例、原料和晶化条件同实施例5，不同的是将原料中的三甲胺用三乙醇胺替代。合成样品为SAPO-5和SAPO-34的物理混合物，XRD结果见图6。
对比例8
具体配料摩尔比例、原料和晶化条件同实施例5，不同的是省去原料中的三甲胺的添加。合成样品为无定形，XRD分析结果见图6。
对比例3-8的合成结果显示本专利申请的具有GME和CHA共晶的Cu-SAPO分子筛，只有在特定的模板剂组合及适宜的晶化条件下才能够得到。
本申请虽然以较佳实施例公开如上，但并不用来限定权利要求，任何本领域技术人员在不脱离本申请构思的前提下，都可以做出若干可能的变动和修改，因此本申请的保护范围应当以本申请权利要求所界定的范围为准。

Claims (10)

  1. 一种具有CHA和GME共生晶相的含铜的磷酸硅铝(SAPO)分子筛，其特征在于，所述分子筛的X射线衍射图谱至少含有以下衍射峰：
    Figure PCTCN2017074985-appb-100001
  2. 根据权利要求1中所述的分子筛，其特征在于，分子筛的无机骨架具有如下的化学组成：wCu-(SixAlyPz)O2，其中：x、y、z分别表示Si、Al、P的摩尔分数，其范围分别是x＝0.01～0.28，y＝0.35～0.55，z＝0.28～0.50，且x+y+z＝1，w为每摩尔(SixAlyPz)O2对应的Cu的摩尔数，w＝0.001～0.124。
  3. 根据权利要求1所述的分子筛，其特征在于，分子筛包含模板剂的无水化学组成可表示为：wCu·mR1·nR3·(SixAlyPz)O2，其中：R1为二异丙醇胺或二乙醇胺，R3为三甲胺；m为每摩尔(SixAlyPz)O2中R1模板剂的摩尔数，n为每摩尔(SixAlyPz)O2中R3模板剂的摩尔数，m＝0.01～0.20，n＝0.01～0.10；x、y、z分别表示Si、Al、P的摩尔分数，其范围分别是x＝0.01～0.28，y＝0.35～0.55，z＝0.28～0.50，且x+y+z＝1；w为每摩尔(SixAlyPz)O2对应的Cu的摩尔数，w＝0.001～0.124。
  4. 一种合成权利要求1-3中任一项所述的分子筛的方法，其特征在于，包括如下步骤：
    a)将铜源，去离子水、模板剂R1和R2，硅源、铝源和磷源按比例混合，得到具有如下摩尔配比的初始凝胶混合物：
    Cu/Al2O3＝0.01～0.25；
    SiO2/Al2O3＝0.05～2.0；
    P2O5/Al2O3＝0.5～1.5；
    H2O/Al2O3＝8～40；
    R1/Al2O3＝5～20；
    R2/Al2O3＝0.1～1.5；
    其中，R1为二异丙醇胺(DIPA)或二乙醇胺(DEOA)；R2为三甲胺(TMA)、苄基三甲基氯化铵(BTACl)、苄基三甲基氢氧化铵(BTAOH)中的任意一种或任意几种的混合物；
    b)将步骤a)所得初始凝胶混合物装入高压合成釜，密闭，升温到160～220℃，晶化5～72小时；
    c)晶化完成后，固体产物经分离、洗涤、干燥后，即得所述的分子筛。
  5. 根据权利要求4所述的方法，其特征在于，步骤a)的配料过程如下：铜源首先与水混合，然后加入R1和R2，并在室温搅拌0.5-5h，随后依次向混合液中加入铝源，硅源和磷源，并将混合凝胶在室温搅拌1-5h。
  6. 根据权利要求4所述的方法，其特征在于，步骤a)中所述硅源选自硅溶胶、活性二氧化硅、正硅酸酯、偏高岭土中的一种或几种；所述铝源选自铝盐、活性氧化铝、拟薄水铝石、烷氧基铝、偏高岭土中的一种或几种；所述磷源选自正磷酸、磷酸氢铵、磷酸二氢铵、有机磷化物、磷氧化物中的一种或几种；所述铜源选自Cu(OAc)2，CuSO4,Cu(NO3)2，CuCl2中的一种或几种。
  7. 根据权利要求4所述的方法，其特征在于，所述步骤b)中的晶化过程在静态或动态下进行。
  8. 根据权利要求4所述的方法，其特征在于，所述步骤a)初始凝胶混合物中R1/Al2O3＝5.0～10。
  9. 根据权利要求4所述的方法，其特征在于，所述步骤a)初始凝胶混合物中R2/Al2O3＝0.25～1.0。
  10. 一种用于NOx选择还原脱除反应的催化剂，其由根据权利要求1-3中任一项所述的分子筛或根据权利要求4-9中任一项所述的方 法合成的分子筛经550～700℃空气中焙烧得到。
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