CN112760123A - Heavy naphtha desulfurizer and preparation method thereof - Google Patents
Heavy naphtha desulfurizer and preparation method thereof Download PDFInfo
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- CN112760123A CN112760123A CN202011512451.5A CN202011512451A CN112760123A CN 112760123 A CN112760123 A CN 112760123A CN 202011512451 A CN202011512451 A CN 202011512451A CN 112760123 A CN112760123 A CN 112760123A
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- heavy naphtha
- metal oxide
- composite metal
- desulfurizer
- solution
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- 238000002360 preparation method Methods 0.000 title abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 84
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 84
- 239000002131 composite material Substances 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002808 molecular sieve Substances 0.000 claims abstract description 58
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 27
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 17
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 13
- 238000004898 kneading Methods 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 68
- 239000000843 powder Substances 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 239000012065 filter cake Substances 0.000 claims description 32
- 239000002244 precipitate Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006477 desulfuration reaction Methods 0.000 claims description 15
- 230000023556 desulfurization Effects 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 11
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910002706 AlOOH Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 230000003009 desulfurizing effect Effects 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 241000522215 Dipteryx odorata Species 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 abstract description 29
- 239000011593 sulfur Substances 0.000 abstract description 29
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000000746 purification Methods 0.000 abstract description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- 239000012716 precipitator Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000009388 chemical precipitation Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 21
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 14
- 238000000227 grinding Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 102100033118 Phosphatidate cytidylyltransferase 1 Human genes 0.000 description 2
- 101710178747 Phosphatidate cytidylyltransferase 1 Proteins 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100033126 Phosphatidate cytidylyltransferase 2 Human genes 0.000 description 1
- 101710178746 Phosphatidate cytidylyltransferase 2 Proteins 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a heavy naphtha desulfurizer which comprises the following components in percentage by mass: 10 to 50 percent of activated alumina, 10 to 50 percent of molecular sieve and 30 to 60 percent of composite metal oxide; the invention also discloses a preparation method of the heavy naphtha desulfurizer, which comprises the steps of dropwise adding a nitrate solution corresponding to the composite metal oxide into the ammonium salt solution for reaction, drying, roasting to obtain the composite metal oxide, uniformly mixing the composite metal oxide with the carrier raw material, the binder and water, kneading and forming, and drying and roasting in sequence to obtain the heavy naphtha desulfurizer. The heavy naphtha desulfurizer of the invention adopts composite metal oxide combined with active alumina and molecular sieve as carriers, so that the active component composite metal oxide is fully dispersed in the carriers, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved; the invention adopts a chemical precipitation method and takes ammonium carbonate or ammonium bicarbonate as a precipitator, thereby avoiding the introduction of impurity ions and being convenient for industrial production.
Description
Technical Field
The invention belongs to the field of petrochemical catalytic purificant, and particularly relates to a heavy naphtha desulfurizer and a preparation method thereof.
Background
Naphtha is a product of primary or secondary processing of crude oil or other oils by refinery enterprises, and can be classified into light naphtha and heavy naphtha according to the difference of distillation cut points. The heavy naphtha has high potential aromatic hydrocarbon content and low nitrogen and sulfur content, so that the heavy naphtha is the most important raw material for producing high-octane gasoline and aromatic hydrocarbon. In recent years, the heavy naphtha processing equipment has become larger and larger, so that the raw material demand is lowThe number of the supply and demand contradictions is increasing. The refining enterprises carry out hydrocracking treatment on heavy diesel oil, wax oil or mixed diesel wax oil, and simultaneously improve the cut point of heavy naphtha so as to obtain more heavy naphtha raw materials. In the production process of the heavy naphtha, the sulfur content in the heavy naphtha is seriously exceeded due to the heavy raw material and the complication of the sulfur form in the raw material. The analysis shows that the total sulfur content in the heavy naphtha is about 3-5 mug g-1In which H is2The S content accounts for about 70 percent of the total sulfur, and the rest is the mercaptan organic sulfur. The literature data show that when heavy naphtha is used as a raw material for catalytic reforming, the sulfur content in the heavy naphtha is 1. mu.g.g-1When the activity of the reforming catalyst is affected, the liquid yield and hydrogen yield above C5 decrease. When the sulfur content in the heavy naphtha was 1.5. mu.g g-1During the process, the activity of the reforming catalyst is reduced by about 20%, the service cycle of the catalyst is shortened, and the sulfur content in the liquid product exceeds the standard. Similarly, heavy naphthas containing excess sulfide can also poison the isomerization catalyst, resulting in permanent catalyst deactivation. At present, researchers and the industry generally believe that when the sulfur content of heavy naphtha is below 0.5 μ g-1In the meantime, the requirement for reprocessing the raw material can be satisfied, and thus, the heavy naphtha desulfurization technology is regarded as important.
The fixed bed dry desulfurization technology is also applied to the heavy naphtha desulfurization process due to the advantages of simple flow, convenient application and the like. In the 'application of heavy naphtha desulfurization technology', such as strong light irradiation, ZnO desulfurizer is adopted to remove sulfide in heavy naphtha; the results of experiments on the removal of hydrogen sulfide from naphtha by an iron oxide desulfurizer are introduced in 'evaluation of use effect of naphtha desulfurizer'; benyan and the like performed research on regeneration performance of desulfurization adsorbent for heavy naphtha by medium-pressure hydrogenation by using clay/active carbon as a desulfurizing agent. In the technology, the ZnO desulfurizer is suitable for being used at high temperature, and when the ZnO desulfurizer is used at low temperature, the sulfur capacity is low, and the service cycle of the desulfurizer is short; the iron oxide desulfurizer has low desulfurization precision, can not meet the requirement of raw material purification degree, is easy to harden and argillize when meeting water, and influences the service life. Although the activated carbon adsorbent has good removal capacity for sulfur in heavy naphtha, the sulfur capacity is low, frequent regeneration is needed, and the process is complex.
In the prior art, various metal oxide carriers are also used as a naphtha desulfurizer on alumina, for example, chinese patent CN111410986A describes a preparation method of a naphtha fine desulfurizer, the desulfurizer uses copper nitrate, zinc nitrate, aluminum nitrate and nickel nitrate as raw materials to prepare a solution, then sodium carbonate is added to neutralize and precipitate, and after neutralization is finished, the precipitate is filtered, washed, dried and roasted to obtain a heavy naphtha desulfurizer. The method has the following problems: the nitrate solution uses sodium carbonate as a precipitator in the neutralization process, so that undesirable Na is introduced in the preparation process of the desulfurizer+A large amount of water is used for washing and removing in the subsequent process, so that water resources are wasted; in the using process of the industrial desulfurizer, powder is prepared into particles with certain shapes and then is filled into a reactor to reduce the resistance of the reactor, and the forming of the powder has great influence on the pore structure and the activity of the desulfurizer. The desulfurizer powder prepared by the method is not subjected to molding treatment, and has no industrial application value.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a heavy naphtha desulfurizer aiming at the defects of the prior art. According to the heavy naphtha desulfurizer, the uniform mixing degree of each metal oxide in the active components is improved by adopting the composite metal oxide, and the active alumina and the molecular sieve are combined to be adopted as carriers, so that the composite metal oxide is fully dispersed in the active alumina and the molecular sieve, the dispersion degree of the active components is improved, more reactive active sites are provided, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved.
In order to solve the technical problems, the invention adopts the technical scheme that: the heavy naphtha desulfurizer is characterized by comprising the following components in percentage by mass: 10 to 50 percent of activated alumina, 10 to 50 percent of molecular sieve and 30 to 60 percent of composite metal oxide.
Compared with the desulfurizer consisting of one oxide or two oxide powders and alumina powder in the prior art, the heavy naphtha desulfurizer of the invention consists of carrier active alumina, a molecular sieve and active component composite metal oxide, the uniform mixing degree of each metal oxide in the active component is improved by adopting the composite metal oxide, high specific surface area is provided by combining the active alumina, and rich pore channels and proper pore diameter are provided by adopting the molecular sieve, so that the composite metal oxide is fully dispersed in the active alumina and the molecular sieve, the dispersion degree of the active component is improved, more reactive active sites are provided, the desulfurization performance of the heavy naphtha desulfurizer is improved, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved.
The heavy naphtha desulfurizer is characterized in that the active alumina is gamma-Al2O3Or AlOOH. nH2And O. The optimized active alumina has large specific surface area and high pore volume, is more beneficial to the diffusion and reaction of liquid phase material heavy naphtha, and realizes better desulfurization effect.
The heavy naphtha desulfurizer is characterized in that the molecular sieve is at least one of ZSM-5, Y-type and 13X molecular sieves. The optimized molecular sieve has uniform pore paths and regular arrangement, and particularly, the pore diameters of the three molecular sieves are matched with those of the liquid phase material heavy naphtha, so that the adsorption and removal of hydrogen sulfide are facilitated.
The heavy naphtha desulfurizer is characterized in that the metal elements of the composite metal oxide include two or three of copper, zinc, magnesium, calcium, nickel, iron and manganese. The corresponding desulfurization reaction temperatures of the oxides of the optimized metal elements are different, namely the corresponding desulfurization reaction temperatures are good at high temperature and the corresponding desulfurization reaction temperatures are good at low temperature, the invention adopts the composition of the oxides of 2 or 3 metal elements, takes account of the desulfurization reaction at high and low temperatures, and is favorable for the dispersion of the composite metal oxides, so that the heavy naphtha desulfurizer prepared by the composition has stronger adaptability to raw materials and process conditions.
In addition, the invention also discloses a method for preparing the heavy naphtha desulfurizer, which comprises the following steps:
dissolving nitrates of two or three metal elements of copper, zinc, magnesium, calcium, nickel, iron and manganese in deionized water, and then heating to 40-70 ℃ to obtain a solution A;
dissolving ammonium salt in deionized water, and heating to 30-50 ℃ to obtain a solution B;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7-10, then heating to 70-90 ℃, standing for 30-120 min, and carrying out suction filtration and washing on the obtained precipitate to obtain a filter cake;
step four, drying the filter cake obtained in the step three, and then roasting to obtain a composite metal oxide;
and step five, adding the composite metal oxide obtained in the step four, active alumina powder, molecular sieve raw powder, dry powder of an organic binder and water into a mixer, uniformly mixing and kneading to obtain a strip material to be extruded, then placing the strip material to be extruded into a forming machine for strip extrusion forming to obtain a strip material, and then drying and roasting the strip material in sequence to obtain the heavy naphtha desulfurizer.
The invention adopts a chemical precipitation method, takes ammonium salt as a precipitator, performs acid-base neutralization reaction with nitrate of metal elements, simultaneously performs molecular rearrangement and secondary crystallization, has uniform crystal grain size, and obtains a precipitate with a composite metal oxide precursor as a main component, because NH in the ammonium salt4 +And NO3 -Is easily dissolved in water, and then the precipitate can be washed by only a small amount of water to remove most of precipitator components adsorbed in the precipitate, namely NH4 +And NO3 -To obtain a filter cake, a small part of NH remaining in the filter cake4 +And NO3 -The catalyst is easy to decompose and remove in the subsequent roasting process, thereby avoiding introducing impurity ions into the heavy naphtha desulfurizer, reducing the washing times, saving the water consumption and facilitating the industrial production; meanwhile, the composite metal oxide obtained by roasting the filter cake, active alumina powder and molecular sieve raw powder are mixed, molded, dried and roasted, and are highly dispersed into the heavy naphtha desulfurizer to form uniformly distributed active sites, and the active alumina with large specific surface area and the molecules with rich pore channelsThe sieve has strong adsorption and diffusion capacity to hydrogen sulfide and mercaptan, effectively promotes the reaction and removal capacity of the composite metal oxide to the sulfide, and greatly improves the purification degree and the sulfur capacity of the heavy naphtha desulfurizer.
The method is characterized in that the total molar concentration of the metal ions in the solution A in the step one is 0.1mol/L-1～1.0mol/L-1. By controlling the total molar concentration of the metal ions in the solution A, the reaction rate in the subsequent heating and standing process is favorably and effectively controlled, so that a precipitate with better crystallinity is obtained.
The method is characterized in that the ammonium salt in the step two is ammonium carbonate or ammonium bicarbonate, and the mass concentration of the solution B is 10-15%. The mass concentration of the solution B is controlled to effectively control the reaction rate in the subsequent heating and standing process, so that the precipitate with better crystallinity is obtained.
The method is characterized in that the drying temperature in the fourth step and the drying temperature in the fifth step are both 80-120 ℃ and the drying time is 8-12 hours, the roasting temperature is 300-500 ℃ and the roasting time is 4-6 hours. The drying and roasting process parameters are respectively favorable for fully volatilizing water in the filter cake and fully decomposing organic matters in the composite metal oxide, so that a uniform mesoporous structure is formed.
The method is characterized in that in the fifth step, the organic binder is carboxymethyl cellulose, sesbania powder or tonka-bean powder, and the mass of the organic binder is 3% of the total mass of the composite metal oxide, the activated alumina powder, the molecular sieve raw powder and the dry powder of the organic binder. The preferred type of the binder has moderate molecular weight and good cohesiveness, and simultaneously can form a mesoporous pore channel after being decomposed into gas at high temperature and escaping, thereby improving the pore structure of the desulfurizer.
The method is characterized in that in the fifth step, the mixer is a kneader or a material grinding machine, and the time for uniformly mixing is 20-30 min; the forming machine is a screw rod extruding machine or an oil pressure extruding machine. The optimized time for uniform mixing fully ensures that all materials are uniformly mixed, saves the production time and improves the production efficiency.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the uniform mixing degree of each metal oxide in the active components is improved by adopting the composite metal oxide, and the active alumina and the molecular sieve are combined to be used as carriers, so that the composite metal oxide is fully dispersed in the active alumina and the molecular sieve, the dispersion degree of the active components is improved, more reaction active sites are provided, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved.
2. The invention adopts a chemical precipitation method and takes ammonium salt as a precipitator, and NH in the ammonium salt is utilized4 +And NO in metal nitrates3 -The catalyst is easy to dissolve in water, and a small amount of water is used for washing and subsequent roasting to remove the residual precipitant while the neutralization reaction is realized, so that impurity ions are prevented from being introduced into the desulfurizer, and the industrial production is facilitated.
3. The composite metal oxide, the active alumina powder and the molecular sieve raw powder are mixed, molded, dried and roasted to be highly dispersed in the desulfurizer to form uniformly distributed active sites, and the active alumina with large specific surface area and the molecular sieve with rich pore channels have strong adsorption and diffusion capacities on hydrogen sulfide and mercaptan, so that the reaction removal capacity of the composite metal oxide on sulfide is further promoted, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are greatly improved.
4. The heavy naphtha desulfurizer prepared by the invention has the advantages of large specific surface, high sulfur capacity, strong adaptability to raw materials, stable performance and easy industrial production.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al2O350 percent, 10 percent of ZSM-5 molecular sieve and 40 percent of composite metal oxide; the metal elements in the composite metal oxide are copper and nickel.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 1000g of copper nitrate and 500g of nickel nitrate in deionized water, and then heating to 40 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 0.1mol/L-1；
Step two, dissolving 650g of ammonium carbonate in deionized water, and then heating to 50 ℃ to obtain a solution B with the mass concentration of 10%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7, then heating to 70 ℃, standing for 30min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 80 ℃ for 12h, and then roasting at 300 ℃ for 6h to obtain a composite metal oxide;
step five, mixing 640g of the composite metal oxide obtained in the step four with 800g of gamma-Al2O3Adding 150g of ZMS-5 molecular sieve raw powder, 48g of carboxymethyl cellulose and 650mL of water into a kneader, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for extrusion molding to obtain a strip material with phi 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 120 ℃ for 8h, and roasting at 500 ℃ for 4h to obtain the heavy naphtha desulfurizer which is recorded as DS-1.
Example 2
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: AlOOH nH210% of O, 50% of 13X molecular sieve and 40% of composite metal oxide; the metal elements in the composite metal oxide are copper, zinc and nickel.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 500g of copper nitrate, 600g of zinc nitrate and 200g of nickel nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 0.5mol/L-1；
Step two, dissolving 600g of ammonium carbonate in 4200mL of deionized water, and then heating to 30 ℃ to obtain a solution B with the mass concentration of 12.5%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8.5, then heating to 90 ℃, standing for 75min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 100 ℃ for 10 hours, and then roasting at 400 ℃ for 5 hours to obtain a composite metal oxide;
step five, mixing 550g of the composite metal oxide obtained in the step four with 230g of AlOOH & nH2Adding O, 700g of 13X molecular sieve raw powder, 45g of sesbania powder and 600mL of water into a kneader, uniformly mixing and kneading for 25min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 80 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the heavy naphtha desulfurizer which is marked as DS-2.
Example 3
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al2O335 percent, 35 percent of Y-type molecular sieve and 30 percent of composite metal oxide; the metal elements in the composite metal oxide are manganese, iron and nickel.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 450g of manganese nitrate, 450g of ferric nitrate and 420g of nickel nitrate in deionized water, and then heating to 55 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Step two, dissolving 600g of ammonium carbonate in 3400mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 15%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8.5, then heating to 80 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 120 ℃ for 8 hours, and then roasting at 500 ℃ for 4 hours to obtain a composite metal oxide;
step five, 688g of the composite metal oxide obtained in the step four and 800g of gamma-Al2O3Adding 700g of Y-type molecular sieve raw powder, 70g of tonka bean powder and 950mL of water into a grinding machine, uniformly mixing and kneading for 30min to obtain a material to be extruded, then placing the material to be extruded into a double-screw extruder for extrusion molding to obtain a strip material with phi of 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 80 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain a heavy naphtha desulfurizer which is recorded as DS-3.
Example 4
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: AlOOH nH220% of O, 10% of 13X molecular sieve, 10% of Y-type molecular sieve and 60% of composite metal oxide; the metal elements in the composite metal oxide are copper, iron and manganese.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, 600g of copper nitrate, 600g of ferric nitrate and 500g of manganese nitrate are dissolved in deionized water, and then heated to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Dissolving 900g of ammonium carbonate in 5100mL of deionized water, and heating to 50 ℃ to obtain a solution B with the mass concentration of 15%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 10, then heating to 90 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 110 ℃ for 10h, and then roasting at 450 ℃ for 5h to obtain a composite metal oxide;
step five, 895g of the composite metal oxide obtained in the step four and 400g of AlOOH & nH2Adding O, 150g of 13X molecular sieve raw powder, 150g of Y-type molecular sieve powder, 45g of carboxymethyl cellulose and 600mL of water into a material grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruding machine for strip extrusion molding to obtain a strip material with phi of 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 110 ℃ for 10h, and roasting at 350 ℃ for 6h to obtain a heavy naphtha desulfurizer which is recorded as DS-4.
Example 5
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al2O327.5 percent of Y-type molecular sieve, 17.5 percent of ZMS-5 molecular sieve and 45 percent of composite metal oxide; the metal elements in the composite metal oxide are copper, calcium and zinc.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 500g of copper nitrate, 600g of calcium nitrate and 400g of zinc nitrate in deionized water, and then heating to 60 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Step two, dissolving 700g of ammonium carbonate in 6300mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 10%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 10, then heating to 80 ℃, standing for 90min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 90 ℃ for 10h, and then roasting at 450 ℃ for 6h to obtain a composite metal oxide;
step five, 590g of the composite metal oxide obtained in the step four and 350g of gamma-Al2O3225g of Y-type molecular sieve raw powder, 125g of ZMS-5 molecular sieve, 40g of carboxymethyl cellulose and 650mL of water are added into a material grinding machine to be uniformly mixed and kneaded for 15min to obtain the material to be extrudedAnd (3) strip materials are placed in a double-screw rod extruder to be extruded and molded to obtain strip materials with the diameter of phi 3mm multiplied by 5mm (the diameter is multiplied by the length), the strip materials are dried at the temperature of 120 ℃ for 8 hours and are roasted at the temperature of 400 ℃ for 5 hours to obtain the heavy naphtha desulfurizer which is recorded as DS-5.
Example 6
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al2O343 percent of ZSM-5 molecular sieve, 9 percent of Y-type molecular sieve, 9 percent of 13X molecular sieve and 30 percent of composite metal oxide; the metal elements in the composite metal oxide are zinc and iron.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 500g of zinc nitrate and 400g of ferric nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Step two, dissolving 330g of ammonium bicarbonate in 1900mL of deionized water, and then heating to 50 ℃ to obtain a solution B with the mass concentration of 15%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7, then heating to 85 ℃, standing for 100min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 110 ℃ for 12h, and then roasting at 450 ℃ for 6h to obtain a composite metal oxide;
step five, mixing 340g of the composite metal oxide obtained in the step four with 500g of gamma-Al2O3100g of ZMS-5 molecular sieve raw powder, 100g of Y-type molecular sieve raw powder, 100g of 13X molecular sieve raw powder, 35g of sesbania powder and 450mL of water are added into a grinding machine to be uniformly mixed and kneaded for 20min to obtain a strip material to be extruded, then the strip material to be extruded is placed into an oil pressure strip extruding machine to be extruded and molded to obtain a strip material with phi of 3mm multiplied by 5mm (diameter multiplied by length), the strip material is dried at 110 ℃ for 12h and roasted at 450 ℃ for 6h to obtain a heavy naphtha desulfurizer which is recorded as DS-6.
Example 7
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al2O323 percent, 13X molecular sieve 37 percent and composite metal oxide 40 percent; the metal elements in the composite metal oxide are magnesium and copper.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 700g of magnesium nitrate and 800g of copper nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Step two, dissolving 650g of ammonium carbonate in 3680mL of deionized water, and then heating to 50 ℃ to obtain a solution B with the mass concentration of 15%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7.5, then heating to 85 ℃, standing for 90min, carrying out suction filtration on the obtained precipitate, and washing for 4 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 100 ℃ for 12 hours, and then roasting at 450 ℃ for 6 hours to obtain a composite metal oxide;
step five, mixing 530g of the composite metal oxide obtained in the step four with 300g of gamma-Al2O3Adding 500g of 13X molecular sieve raw powder, 27g of tonka bean powder and 550mL of water into a grinding machine, uniformly mixing and kneading for 20min to obtain a material to be extruded, then placing the material to be extruded into a double-screw extruder for extrusion molding to obtain a strip material with phi of 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 80 ℃ for 12h, and roasting at 350 ℃ for 6h to obtain a heavy naphtha desulfurizer which is recorded as DS-7.
Example 8
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: AlOOH nH2O36%, 13X molecular sieve 14% and composite metal oxide 50%; the metal elements in the composite metal oxide are calcium and nickel.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 1000g of calcium nitrate and 500g of nickel nitrate in deionized water, and then heating to 60 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Step two, dissolving 700g of ammonium carbonate in 4900mL of deionized water, and then heating to 50 ℃ to obtain a solution B with the mass concentration of 12.5%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 10, then heating to 80 ℃, standing for 60min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 120 ℃ for 8 hours, and then roasting at 500 ℃ for 4 hours to obtain a composite metal oxide;
step five, 546g of the composite metal oxide obtained in the step four and 540g of AlOOH & nH2Adding O, 150g of 3X molecular sieve raw powder, 30g of carboxymethyl cellulose and 500mL of water into a kneader, uniformly mixing and kneading for 30min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 120 ℃ for 8h, and roasting at 450 ℃ for 6h to obtain the heavy naphtha desulfurizer which is recorded as DS-8.
Example 9
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al2O330 percent, 10 percent of Y-type molecular sieve and 60 percent of composite metal oxide; the metal elements in the composite metal oxide are copper and zinc.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 1000g of copper nitrate and 950g of zinc nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Step two, dissolving 850g of ammonium carbonate in 7650mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 10%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8, then heating to 85 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 110 ℃ for 10h, and then roasting at 350 ℃ for 6h to obtain a composite metal oxide;
step five, mixing 830g of the composite metal oxide obtained in the step four with 410g of gamma-Al2O3Adding 135g of Y-type molecular sieve raw powder, 30g of carboxymethyl cellulose and 600mL of water into a grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for strip extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 110 ℃ for 12h, and roasting at 450 ℃ for 4h to obtain a heavy naphtha desulfurizer which is recorded as DS-9.
Comparative example 1
The heavy naphtha desulfurizer of the comparative example consists of the following components in percentage by mass: gamma-Al2O330 percent of bentonite, 10 percent of bentonite and 60 percent of composite metal oxide; the metal elements in the composite metal oxide are copper and zinc.
The preparation method of the heavy naphtha desulfurizer of the comparative example comprises the following steps:
step one, dissolving 1000g of copper nitrate and 950g of zinc nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Step two, dissolving 850g of ammonium carbonate in 7650mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 10%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8, then heating to 85 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 110 ℃ for 10h, and then roasting at 350 ℃ for 6h to obtain a composite metal oxide;
step five, mixing 830g of the composite metal oxide obtained in the step four with 410g of gamma-Al2O3144g of bentonite, 30g of carboxymethyl cellulose and 600mL of water are added into a material grinding machine to be uniformly mixed and kneaded for 20min to obtain a material to be extruded, then the material to be extruded is placed into a double-screw extruder to be extruded and molded to obtain a material with phi of 3mm multiplied by 5mm (diameter multiplied by length), the material is dried at 110 ℃ for 12h and roasted at 450 ℃ for 4h to obtain a heavy naphtha desulfurizer which is marked as CDS-1.
Comparative example 2
The heavy naphtha desulfurizer of the comparative example consists of the following components in percentage by mass: gamma-Al2O330 percent of Y-type molecular sieve, 10 percent of copper oxide and 30 percent of zinc oxide.
The preparation method of the heavy naphtha desulfurizer of the comparative example comprises the following steps: 415g of copper oxide powder, 415g of zinc oxide powder and 410g of gamma-Al2O3Adding 135g of Y-type molecular sieve raw powder, 30g of carboxymethyl cellulose and 600mL of water into a grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for strip extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 110 ℃ for 12h, and roasting at 450 ℃ for 4h to obtain a heavy naphtha desulfurizer which is recorded as CDS-2.
Comparative example 3
The heavy naphtha desulfurizer of the comparative example consists of the following components in percentage by mass: gamma-Al2O330 percent, 10 percent of Y-type molecular sieve and 60 percent of composite metal oxide; the metal elements in the composite metal oxide are copper and zinc.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 1000g of copper nitrate and 950g of zinc nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the solution AThe total molar concentration of the metal ions in the solution is 1.0mol/L-1；
Step two, dissolving 850g of sodium carbonate in 7650mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 10%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8, then heating to 85 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 110 ℃ for 10h, and then roasting at 350 ℃ for 6h to obtain a composite metal oxide;
step five, mixing 830g of the composite metal oxide obtained in the step four with 410g of gamma-Al2O3Adding 135g of Y-type molecular sieve raw powder, 30g of carboxymethyl cellulose and 600mL of water into a grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for strip extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 110 ℃ for 12h, and roasting at 450 ℃ for 4h to obtain a heavy naphtha desulfurizer which is recorded as CDS-3.
Example 10
The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al2O335 percent, 13X type molecular sieve 20 percent and composite metal oxide 45 percent; the metal elements in the composite metal oxide are copper and iron.
The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:
step one, dissolving 400g of copper nitrate and 600g of ferric nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L-1；
Step two, dissolving 450g of ammonium carbonate in 2550mL of deionized water, and then heating to 30 ℃ to obtain a solution B with the mass concentration of 15%;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7, then heating to 80 ℃, standing for 60min, carrying out suction filtration on the obtained precipitate, and washing for 4 times by using deionized water to obtain a filter cake;
step four, drying the filter cake obtained in the step three at 120 ℃ for 8 hours, and then roasting at 350 ℃ for 6 hours to obtain a composite metal oxide;
step five, 560g of the composite metal oxide obtained in the step four and 450g of gamma-Al2O3Adding 250g of 13X type molecular sieve raw powder, 25g of carboxymethyl cellulose and 500mL of water into a material grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruding machine for strip extrusion molding to obtain a strip material with phi 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 100 ℃ for 10h, and roasting at 400 ℃ for 4h to obtain a heavy naphtha desulfurizer which is recorded as DS-10.
Respectively crushing the heavy naphtha desulfurizer in the embodiments 1 to 10 and the comparative examples 1 to 3 to 20 meshes, respectively weighing 3mL of the heavy naphtha desulfurizer, filling the heavy naphtha into a middle constant-temperature zone of a stainless steel reactor with the diameter of 10mm multiplied by 600mm (diameter multiplied by length), filling two ends of the stainless steel reactor with 20 to 40 meshes of quartz sand, desulfurizing the heavy naphtha at the reaction temperature of 150 ℃, the pressure of normal pressure and the feeding amount of the heavy naphtha of 20mL/h, and inspecting the purification degree and the sulfur capacity of the heavy naphtha desulfurizer, wherein the content of hydrogen sulfide in the raw material heavy naphtha is 4.75 mu g-1The mercaptan content was 2. mu.g.g-1(ii) a When the total sulfur content at the outlet of the stainless steel reactor exceeds 0.5 mu g-1When the oil is considered to have penetrated, the desulfurization treatment is stopped, the desulfurizing agent is taken out and the sulfur capacity of each heavy naphtha desulfurizing agent is analyzed, and the results are shown in the following table 1.
The sulfur capacity calculation formula is as follows:
in the formula: s- -sulfur capacity, which represents the capacity of the desulfurizing agent to remove hydrogen sulfide, unit%
C1- - -stainless steelSulfur content in units of ug g in heavy naphtha at reactor inlet-1；
C2Sulfur content in units of mug at the outlet of a stainless steel reactor-1；
Q- - -total mass of heavy naphtha passing through the desulfurizer at breakthrough, in g;
m is the weight of the heavy naphtha desulfurizer, unit g.
TABLE 1
Note: the total sulfur content in table 1 was measured by coulometry, and the sulfur capacity was measured by combustion.
As can be seen from table 1, the heavy naphtha desulfurizer in examples 1 to 10 of the present invention has a good reaction removal capability for sulfides, and greatly improves the purification degree and sulfur capacity of the heavy naphtha desulfurizer; the sulfur capacity and the purification degree of the heavy naphtha desulfurizer DS-9 in example 9 are higher than those of CDS-1 to CDS-3 in comparative examples 1 to 3, which shows that the invention adopts the composite metal oxide to improve the uniform mixing degree of each metal oxide in the active component, and combines the active alumina and the molecular sieve as the carrier, so that the composite metal oxide is fully dispersed in the active alumina and the molecular sieve, the dispersion degree of the active component is improved, more reaction active sites are provided, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.
Claims (10)
1. The heavy naphtha desulfurizer is characterized by comprising the following components in percentage by mass: 10 to 50 percent of activated alumina, 10 to 50 percent of molecular sieve and 30 to 60 percent of composite metal oxide.
2. The heavy naphtha desulfurizer as claimed in claim 1, wherein the activated alumina is γ -Al2O3Or AlOOH. nH2O。
3. The heavy naphtha desulfurization agent according to claim 1, wherein the molecular sieve is at least one of ZSM-5, Y type and 13X molecular sieve.
4. The heavy naphtha desulfurizing agent according to claim 1, wherein the metal elements of said complex metal oxide include two or three of copper, zinc, magnesium, calcium, nickel, iron and manganese.
5. A process for preparing a heavy naphtha desulfurization agent as set forth in any one of claims 1 to 4, which comprises the steps of:
dissolving nitrates of two or three metal elements of copper, zinc, magnesium, calcium, nickel, iron and manganese in deionized water, and then heating to 40-70 ℃ to obtain a solution A;
dissolving ammonium salt in deionized water, and heating to 30-50 ℃ to obtain a solution B;
step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7-10, then heating to 70-90 ℃, standing for 30-120 min, and carrying out suction filtration and washing on the obtained precipitate to obtain a filter cake;
step four, drying the filter cake obtained in the step three, and then roasting to obtain a composite metal oxide;
and step five, adding the composite metal oxide obtained in the step four, active alumina powder, molecular sieve raw powder, dry powder of an organic binder and water into a mixer, uniformly mixing and kneading to obtain a strip material to be extruded, then placing the strip material to be extruded into a forming machine for strip extrusion forming to obtain a strip material, and then drying and roasting the strip material in sequence to obtain the heavy naphtha desulfurizer.
6. The method according to claim 5, wherein the total molar concentration of metal ions in the solution A in the first step is 0.1mol/L-1～1.0mol/L-1。
7. The method according to claim 5, wherein the ammonium salt in the second step is ammonium carbonate or ammonium bicarbonate, and the mass concentration of the solution B is 10-15%.
8. The method according to claim 5, wherein the drying temperature in the fourth step and the drying temperature in the fifth step are both 80-120 ℃ and the drying time is 8-12 h, and the roasting temperature is 300-500 ℃ and the drying time is 4-6 h.
9. The method as claimed in claim 5, wherein the organic binder in step five is carboxymethyl cellulose, sesbania powder or tonka bean powder, and the mass of the organic binder is 3% of the total mass of the composite metal oxide and the dry powder of the activated alumina powder, the molecular sieve raw powder and the organic binder.
10. The method according to claim 5, wherein in the fifth step, the mixer is a kneader or a grinder, and the mixing time is 20min to 30 min; the forming machine is a screw rod extruding machine or an oil pressure extruding machine.
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