CN107096552A - A kind of catalyst and preparation method for FCC gasoline removal of mercaptans - Google Patents
A kind of catalyst and preparation method for FCC gasoline removal of mercaptans Download PDFInfo
- Publication number
- CN107096552A CN107096552A CN201710412089.6A CN201710412089A CN107096552A CN 107096552 A CN107096552 A CN 107096552A CN 201710412089 A CN201710412089 A CN 201710412089A CN 107096552 A CN107096552 A CN 107096552A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- alumina support
- content
- carrier
- alumina
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 239000003502 gasoline Substances 0.000 title claims abstract description 48
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 53
- 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 177
- 239000011148 porous material Substances 0.000 claims abstract description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 31
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011574 phosphorus Substances 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 14
- 239000002671 adjuvant Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 69
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 50
- 229920001661 Chitosan Polymers 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 30
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 26
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000395 magnesium oxide Substances 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000004411 aluminium Substances 0.000 claims description 21
- 229910052684 Cerium Inorganic materials 0.000 claims description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910001593 boehmite Inorganic materials 0.000 claims description 16
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 11
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- 239000011259 mixed solution Substances 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000001404 mediated effect Effects 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 20
- 150000001993 dienes Chemical class 0.000 abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 30
- 229910052717 sulfur Inorganic materials 0.000 description 30
- 239000011593 sulfur Substances 0.000 description 30
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 25
- 150000001336 alkenes Chemical class 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000003921 oil Substances 0.000 description 21
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- 239000002131 composite material Substances 0.000 description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 17
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- -1 zeolite imidazole class Chemical class 0.000 description 9
- 239000011805 ball Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
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- 239000002245 particle Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 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 5
- 239000004964 aerogel Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
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- 235000011054 acetic acid Nutrition 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
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Classifications
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- 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
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The present invention relates to a kind of catalyst for FCC gasoline removal of mercaptans, catalyst includes the alumina support with macroporous structure and the metal active constituent nickel and molybdenum that are carried on carrier, by weight percentage, alumina support with macroporous structure is 66 91wt%, contain adjuvant component phosphorus and magnesium, the 180nm of pore-size distribution 60, macropore ratio 2 75% in carrier, the 2.0ml/g of pore volume 0.8, the 300m of specific surface area 2502/g.Nickel oxide content is 5 19wt%, and oxidation molybdenum content is 2 15wt%.Catalyst tool removal of mercaptans activity is high, and diolefin hydrogenation selectivity is high, and loss of octane number is low.
Description
Technical field
It is used for FCC gasoline mercaptan-eliminating catalyst and preparation method the present invention relates to one kind.
Background technology
Increasingly strict with environmental regulation, countries in the world propose increasingly stricter to the quality of refinery products
It is required that, the particularly limitation to refinery products sulfur content is more and more stricter.Contained vulcanization owner in oils
To be mercaptan (RSH), thioether (RSR) etc., wherein influence of the mercaptan to product quality is maximum, very strong not only with foul smell
Corrosivity, can also influence the stability of product.
CN1229838A discloses a kind of method for transformation of hydrocarbon ils, and this method is to be catalyzed feedstock oil and a kind of hydrofinishing
Agent removal of mercaptans under the process conditions of hydro-sweetening, the Hydrobon catalyst contains the oxygen of load on the alumina support
Change tungsten (molybdenum), nickel oxide and cobalt oxide, the wherein content of tungsten oxide (molybdenum) is 4-10wt%, and the content of nickel oxide is 1-5wt%,
The content of cobalt oxide is 0.01-0.1wt%, and the ratio between the total atom number of nickel and cobalt and nickel, cobalt, total atom number of tungsten (molybdenum) are 0.3-
0.9.CN102451694A discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalyst is with aluminum oxide
Or silicon-containing alumina is carrier, using phosphorus as adjuvant component, using copper and zinc as active component, on the basis of catalyst quality, auxiliary agent
The content of phosphorus is 0.5-3.0wt%, and the content of zinc oxide is 3-15wt%, and the content of cupric oxide is 5-30wt%.Because of the catalysis
Agent has very strong hydrogenation activity, and when for handling full cut FCC gasoline, mercaptans content is reduced to 3 μ g/g by 38 μ g/g, together
When olefin(e) centent 20v% is also reduced to by 25v%, RON losses are up to 1.3 units.CN00136870.2 provides a kind of use
Selectively mercaptan-eliminating catalyst of mercaptan sulfur and preparation method thereof in removing aviation fuel.Catalyst count by weight including
Following component:1. molybdenum oxide 7-20；2. cobalt oxide 0.1-5；3. nickel oxide 0-5 4. silica 0-10；5. phosphorus or boron or fluorine 0-
4；6. aluminum oxide 0-40；7. titanium dioxide 60-100.The preparation method of catalyst is that catalyst carrier maceration extract is impregnated into 1-2
Hour, then dried at 100-130 DEG C；It is last to obtain catalyst within 2-6 hours in 400-550 DEG C of roasting.This catalyst pair
Mercaptan sulfur in jet fuel has good removal effect and preferable low temperature active.CN201210393263.4 is related to a kind of new
The preparation method and application of type demercaptaning for gasoline adsorbent.The preparation method of the demercaptaning for gasoline adsorbent comprises the following steps：
Solvent, metal ion presoma, mesoporous material are well mixed, are aged, organic ligand is added, hydrothermal crystallizing processing is carried out；So
Afterwards, the product to hydrothermal crystallizing processing carries out suction filtration, washing, dried, and obtains zeolite imidazole class framework material/mesoporous material and is combined
Thing；Compression molding, crushing and screening are carried out to the zeolite imidazole class framework material/mesoporous material compound, gasoline desulfurization is obtained
Alcohol adsorbent.In zeolite imidazole class framework material/mesoporous material compound that the present invention is provided, zeolite imidazole class framework material
Specific surface area is high, while being in high dispersion state on mesoporous material, efficiently solves the diffusion limitation reunited and caused.It is described molten
Agent is one or more of combinations in deionized water, methanol, ethanol and DMF；The metal ion is
Zn2+、Cu2+And Co2+In one or more of combinations；The metal ion presoma is the nitrate and/or second of metal ion
One or more of combinations in hydrochlorate；The organic ligand is in imidazoles, 2-methylimidazole, 2- nitroimidazoles and benzimidazole
One or more；The mesoporous material is modified ordered mesoporous molecular sieve.CN200910082945.1 is related to one kind and urged
Change cracking gasoline selective hydrocatalyst and preparation method thereof.Catalyst of the present invention is by Al2O3-TiO2Composite oxide carrier
With reactive metal oxides composition, based on the percentage by weight to catalyst, the NiO contents in its reactive metal oxides are
10-20w%, MoO3Content is 5-12w%；Wherein carrier Al2O3-TiO2Oxide TiO2：Al2O3Weight ratio be 0.01-1：
1.Catalyst of the present invention is in low temperature (100-200 DEG C), low pressure (1-3.0MPa), low hydrogen/gasoline ratio (hydrogen to oil volume ratio 5：1-100：1)
Under conditions of, catalytically cracked gasoline is handled, very high de- diolefin and removal of mercaptans activity, selectivity and stability is shown.
CN200910187903.4 discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalyst is with HZSM-5
Molecular sieve is main carrier component, using copper and zinc as active component.Active component is in terms of oxide weight, and the content of cupric oxide is
5%-27%, the content of zinc oxide is 3%-15%, is prepared using saturation total immersion technology.The catalyst of the present invention is applied to light
Matter oil product carries out selective hydrodesulfurization alcohol reaction, with removal of mercaptans activity height, the low feature of hydrogenation of olefins activity, and after reaction
Liquid yield is high, loss of octane number is seldom.CN201610187374.8 is provided the light hydrocarbons regulated and controled based on aluminum oxide crystal face and taken off
Mercaptan catalyst and its preparation method, the catalyst are using the gama-alumina after hydro-thermal process of the present invention regulation and control as carrier, with nickel
And molybdenum is active metal.Light hydrocarbons mercaptan-eliminating catalyst of the present invention is high activity and high-selectivity catalyst, and it can use
Macromolecular sulfide is generated with alkadienes effect in being catalyzed mercaptan in light hydrocarbons, and can also be catalyzed the selectivity of diolefin and is added
Hydrogen saturation, compared with existing catalyst, catalyst desulfurizing alcohol activity provided by the present invention is high, diolefin hydrogenation selectivity is high,
And active component is not lost in, not easy in inactivation, thus the catalyst runs cycle is long, with preferable prospects for commercial application.The invention
Gama-alumina after hydro-thermal process regulation and control, as described above, the gama-alumina is characterised by that it has highly exposed (111)
(110) crystal face so that active metal nickel (Ni) and molybdenum (Mo) in catalyst of the present invention can be in the gama-alumina crystal faces
On realize that crystal face selection is preferably loaded, W metal is preferentially supported on newly (111) crystal face of exposure, and metal Mo is preferentially supported on
Newly on (110) crystal face of exposure.Meanwhile, two kinds of active metals also by respectively with modified gama-alumina (111) and
(110) effect of crystal face forms two kinds of different active crystal faces, so as to obtain the light hydrocarbons of high activity and high selectivity
Mercaptan-eliminating catalyst.The catalyst can be in efficient removal liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and coker gasoline etc.
In the case of mercaptan and/or alkadienes in light fraction, retain the alkene in raw material, the octane number RON of gasoline only reduces by 0.3
Point or so, so as to realize the high value added utilization of light hydrocarbons.
The composition and comparision contents of above-mentioned catalyst are more, and preparation technology is complicated, and produce catalyst prod matter in enormous quantities
Amount is difficult control.
Macroporous oxide due to larger pore passage structure, higher specific surface area, good heat endurance, using extensively
In fields such as heterogeneous catalyst, catalyst carrier, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance materials.
The carrier of aluminum oxide with macroporous structure is relatively more.CN03126434.4 discloses a kind of macropore alumina supporter,
Containing aluminum oxide, also containing a kind of halogen, on the basis of carrier total amount, the carrier contains 95-99 weight % aluminum oxide, with member
Element meter, 0.1-5 weight % halogen, its acid amount is less than 0.2 mM/gram.The preparation method of macropore alumina supporter includes will
A kind of precursor of aluminum oxide is molded and is calcined, before shaping and roasting, and the precursor of aluminum oxide is mixed with a kind of expanding agent
Close, the expanding agent includes a kind of organic expanding agent and a kind of halide, sintering temperature is 600-850 DEG C, roasting time 1-10
Hour, the consumption of each component contains final alumina support, on the basis of carrier total amount, 95-99 weight % aluminum oxide,
In terms of element, 0.1-5 weight % halogen.Organic expanding agent is in starch, synthetic cellulose, polymeric alcohol, surfactant
One or more.Synthetic cellulose is in carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxylated cellulose
It is one or more of.One or more of the polymeric alcohol in polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, surfactant is selected from fat
Fat alcohol APEO, fatty alkanol amide, molecular weight are 200-10000 acrylic copolymer, in maleic acid copolymer
It is one or more of.CN201110410339.5 provides a kind of high temperature-resistant active aluminum oxide material and preparation method thereof, described oxygen
Change aluminum to be made by following steps：After macropore boehmite, high viscous boehmite are mixed with additive with water, turning
Speed adds the dilute nitric acid reaction that concentration is 30% to be stirred under 100-1000r/min, to the peptization that pH is 2.0-5.5
During state, 3-6h is aged under the stirring of 80 DEG C of -100 DEG C of temperature, add at room temperature pore creating material stir, it is slurrying, spraying, dry
It is dry, it is calcined at 900 DEG C and aluminum oxide is made.The alumina material has the advantages that to be easy to batch production and high-ratio surface.
It can be kept for a long time than surface in 110m at a temperature of 1000-1100 DEG C2/ more than g；The work of the alumina material preparation method
Skill process is simple, with low cost.Wherein described sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methyl fibre
One kind in dimension element, its consumption is the 0-40% of oxide gross weight in alumina material.《Zhongshan University's journal》(2002,41
(2):Method 121-122) introduced is as follows：A diameter of 600nm polystyrene colloidal crystal microballoon is placed on a buchner funnel, so
The ethanol solution of aluminum nitrate and citric acid is added drop-wise under suction filtration on glue crystalline substance afterwards, allows it fully to penetrate into the gap of microballoon,
Through drying and being calcined, polystyrene moulding is removed, macroporous aluminium oxide is obtained.《Acta PhySico-Chimica Sinica》(2006,22 (7):831-
835) method that granular formwork method prepares three-dimensional ordered macroporous alumina is described, this method is as follows：Emulsion polymerization is used first
Method obtains polystyrene microsphere, and aluminum nitrate plus weak aqua ammonia are made into alumina sol, and both are then stirred into mixed by a certain percentage
Close, it is ultrasonically treated, then through drying and being calcined, obtain macroporous aluminium oxide.CN201010221302.3 (CN102311134A) is open
A kind of spherical integral macroporous alumina and preparation method thereof.This method comprises the following steps：By polymer microballoon emulsion, oxidation
Alumina gel and coagulant are well mixed with certain proportion, and the mixture is scattered in oil phase, form w/o type drop, Ran Houzai
Above-mentioned mixed phase system is heated, makes the alumina sol gelling balling-up in aqueous phase, the gel for isolating shaping from oil phase afterwards is micro-
Ball, then obtain described spherical integral macroporous alumina after aged, dry and roasting in aqueous ammonia medium.The aluminum oxide
Macropore diameter is homogeneous controllable in the range of less than 1 μm, and the size of spheric granules is controllable, and mechanical strength is higher, is molded
Journey is simple and easy to do, is easy to be prepared on a large scale.Polymer microballoon diameter 50-1000nm, the type of polymer microballoon is polystyrene
The esters microballoons such as microballoon, polyaerylic acid N-butyl microballoon, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oil phase is
Organic hydrocarbon.The invention, which is mainly, prepares Integral macroporous alumina, and macropore diameter is homogeneous controllable.Preparation process is used
Lipid microballoon and coagulant etc..Preparation technology is complicated, and reagent raw material used is relatively more.Due to polymer microballoon cause
Alumina support internal gutter structure is blind bore, that is to say, that alumina support internal gutter does not have connectivity.
CN201010221297.6 discloses a kind of preparation method of Integral macroporous alumina.This method comprises the following steps：Aluminium
Source, polyethylene glycol and after low-carbon alcohol and water at least one is well mixed, will low-carbon epoxyalkane add it is described mixed
In compound, Integral macroporous alumina is obtained through aging, immersion, dry and roasting.Preparation method of the invention is simple and easy to apply, ring
Border pollution is small, and its aperture of gained Integral macroporous alumina is controllable at 0.05-10 μm.The monoblock type macropore oxidation that the present invention is provided
Thing can be applied to the fields such as macromolecular heterogeneous catalysis, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance material.
CN201410347665.X discloses a kind of big pore volume, the preparation method of high-strength alumina, by adding polyacrylamide, gathering
The expanding agents such as vinyl alcohol, alkylcellulose, sesbania powder, starch, obtain containing eurypyloue alumina support, the consumption of its expanding agent
The 10-30% of aluminum oxide is accounted for, but specific pore diameter range is not disclosed.Although hard mould agent method can obtain preferable macropore oxidation
Alumina supporter, but the consumption of its template causes processing cost to greatly improve more preferably greater than 20%, the decomposition of a large amount of templates
The demand for development of low-carbon environment-friendly is not met.CN201010509425.7 discloses the side of a kind of hydro-thermal and the common reaming of template
Method, to prepare the alumina support containing macroporous structure, is acted on, the consumption of template can be reduced by the complementary reaming of hydro-thermal
To 3-10%, but auxiliary hydro-thermal causes the rise of energy consumption.CN200310103035.X discloses a kind of macroporous aluminium oxide
Preparation method, reaming is carried out using polyvinyl alcohol, poly- propyl alcohol, polyethylene glycol soft template, by adding 1% polyethylene glycol,
The pore volume that aperture is more than 100nm accounts for the 26.2% of total pore volume.Soft template has the advantages that consumption is low, reaming effect is good, still
Solubility property of the alcohols soft template of higher molecular weight in water is poor, causes it to be used to expanding super large porous aluminum oxide and limited
System.CN200910204238.5 (CN102040235) discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The party
Method comprises the following steps：Monodispersed polymer microballoon is assembled into glue crystal template, certain party legal system is then filled into template
Standby alumina sol, most obtains macroporous aluminium oxide through dry and roasting afterwards.This method can be good at control Alumina gel and
The recombination process of Alumina gel and polymer microballoon, the network structure of alumina gel is not destroyed as far as possible, makes prepared oxidation
Aluminium not only has the macropore duct of three-dimensional order but also with higher specific surface area.The invention is burnt by the appropriateness to template
Small fenestra formed by knot, makes the macropore in material be connected with the macropore of surrounding by 12 small fenestras.The oxidation of the invention
Aluminium is suitable for use as the adsorption and separation material of mink cell focus catalyst carrier and organic macromolecule.Have in catalyst carrier material application
Beneficial to the mass transfer ability of material in the catalyst is improved, be conducive to improving the activity and selectivity of catalyst.
CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, comprises the following steps：1) by surface-active
Agent is dissolved in deionized water, stirring, is used as aqueous phase；2) chelating agent, alumina precursor and n-octyl alcohol are mixed, stirred, as
Oil phase；3) Span80 and pore-foaming agent, stirring are added in oil phase；4) by step 3) gained clarification oil phase be poured into aqueous phase
Continue stirring and emulsifying；5) by step 4) gains vacuum filtration, dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.Should
Microballoon has internal closing macroporous structure, and Microsphere Size is 1 μm -100 μm, and the invention is coagulated using pore-foaming agent with the colloidal sol in emulsion
Glue process obtains the metal porous microballoon with internal closing macroporous structure.Porous microsphere is prepared using phase separation principle.It is internal
It is 50nm-5 μm to close aperture.Inside closing aperture is 50nm-5 μm.Aperture is closing inside the aluminum oxide porous microballoon,
That is alumina support internal gutter does not have connectivity.Pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or poly- third
Olefin(e) acid.The invention has used substantial amounts of surfactant, chelating agent, pore-foaming agent, and preparing raw material is more, and synthesis technique is complicated.
Above macroporous aluminium oxide mainly prepares macropore oxygen using cellulose, polymeric alcohol, polystyrene etc. as expanding agent
Change aluminium.
Alumina support with macropore and mesoporous i.e. composite pore structural also compares many.CN101200297A discloses whole
The preparation method of build macroporous aluminium oxide：Reverse concentrated emulsions method is used to prepare monoblock type using styrene and divinylbenzene as monomer big
Hole organic formwork；Al is prepared using aluminium isopropoxide or boehmite as predecessor2O3The hydrosol；By Al2O3The hydrosol is filled into whole
In body formula macropore organic formwork；Monolithic devices organic/inorganic composite after filling is through drying, in 600 DEG C of -900 DEG C of roasting removings
Template, obtains integral macroporous alumina.The advantage of this method is that preparation process is simple and easy to apply, obtained monoblock type macropore oxygen
Changing aluminium has the macropore duct that micron order is interconnected, and aperture is 1-50 μm.It is simple that this method prepares Integral macroporous alumina
It is easy, but the volume fraction of aqueous phase accounts for 75%-90% in this method, and correspondingly the volume fraction of organic monomer is relatively low, this
Method is while organic monomer consumption is reduced, and the preparation efficiency of prepared template is relatively low, is unfavorable for subsequent step macropore
It is prepared by the batch of aluminum oxide.A kind of preparation methods of the alumina support of composite pore structural of CN201110032234.0, including will
Being closed containing calorize selected from least one of aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, aluminium chloride, Alumina gel and boehmite powder
Thing and composite mould plate agent are mixed and are calcined, the composite mould plate agent be mesoporous template and macroporous granules template, it is described mesoporous
Template is selected from polyethylene glycol propane diols-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, cetyl
At least one of trimethylammonium bromide, laurate, stearic acid and AEO, the macroporous granules template are selected from
Polystyrene microsphere, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or the heavy oil that particle diameter is more than 50nm are residual
Slag；The weight ratio of the mesoporous template, macroporous granules template and aluminum contained compound is 0.1-2:0.1-0.7:1, wherein institute
The weight of aluminum contained compound is stated in terms of aluminum oxide.The invention also discloses have mesopore orbit while preparation by the above method
With the alumina support in macropore duct, its intermediary hole accounts for the 40%-90% of total pore volume, and macropore accounts for the 10%-60% of total pore volume.
CN201210328824.2 discloses a kind of method for preparing solid phase of gradient distribution hole gama-alumina.This method is anti-by solid phase
Precursor aluminium carbonate ammonium should be obtained, the gamma oxidation of a kind of high specific surface area, gradient distribution hole and larger pore volume is obtained after roasting
Aluminium.What the present invention was protruded the most is technically characterized in that using raw material solid phase reactive synthesis technique, as obtained by being controlled synthesis condition
The property of gama-alumina.Meanwhile, the inventive method is simple, it is easy to operate, it is not necessary to add expanding agent, cost-effective, is adapted to work
Industryization is produced in batches.The preparation process of alumina support of the present invention comprises the following steps：(1) aluminum nitrate, ammonium hydrogen carbonate and table
Face activating agent is fully ground uniformly, and ageing certain time obtains precursor aluminium carbonate ammonium in the closed container of specified temp；(2)
Aftershaping is well mixed with peptizing agent after precursor aluminium carbonate ammonium obtained by (1) is dried, can typically be squeezed using banded extruder
Bar is molded；(3) it is (2) are obtained that article shaped is dried, final alumina support is made in aerobic roasting.Luring described in step (1)
Lead the polyethylene glycol that agent is liquid form, 0.1-10.0% of the addition equivalent to aluminum nitrate weight.Carbonic acid described in step (2)
The drying process of aluminium ammonium is generally dried 1-20 hours at 50-180 DEG C.Roasting process described in step (3) is in 350-900
It is calcined 1-10 hours at DEG C.The invention prepares gama-alumina using the decomposition at a certain temperature of precursor aluminium carbonate ammonium.Aluminium carbonate
Ammonium produces gas, such as NH in decomposable process3And CO2, the generation and effusion of these gases can manufacture some macropores.Simultaneous oxidation
The pattern of aluminium is transformed by the pattern topology of aluminium carbonate ammonium.Slower heating rate is conducive to gas thing in roasting process
Matter is slowly escaped, and carrier is not easily caused and is caved in.Method is simple, it is not necessary to add any physics expanding agent.
CN201310097588.2 discloses a kind of gama-alumina particle and preparation method thereof：1) aluminum soluble salt is dissolved in by acid
The pH value of acidifying is less than or equal in 3 aqueous solution, and the amount that the aluminum soluble salt is added causes obtained containing aluminium in aluminum water solution
The molar concentration of ion is 0.01-5mol/L；2) to step 1) it is obtained contain in aluminum water solution add alkaline precipitating agent, the alkali
Property precipitating reagent add amount cause reaction after solution ph between 5-12；3) by step 2) obtained mixed sediment solution exists
At room temperature after stirring 0.1-3h, it is put into water-bath or water heating kettle, 6-24h is aged at a temperature of 50-150 DEG C；4) by step
3) after the solution after being aged stirs, dried using spray drying process, it is 150-400 that EAT is controlled during spray drying
DEG C, leaving air temp is 60-110 DEG C, and the thermal efficiency of spray drying is more than 50%；5) by step 4) obtained dried oxidation
Aluminium precursor powder is at room temperature with the first heating rate to 250 DEG C -350 DEG C, then with the second heating rate extremely
400 DEG C -800 DEG C, insulation 0.5-20h obtains final product gama-alumina particle；Wherein, first rate of heat addition is less than the
Two rates of heat addition, and first rate of heat addition and second rate of heat addition are in the range of 0.1-10 DEG C/min.It is obtained
Gama-alumina is experiments verify that test, its specific surface area is in the range of 180m2/g-260m2/g, with high-specific surface area.It is made
Gama-alumina particle observed under ESEM with hollow foam shape pattern, it is and compound with micropore-mesopore-macropore
Aperture structure.So, when gama-alumina is as catalyst carrier, its hollow foam shape pattern can be effectively in dispersed catalyst
Active component.And hollow foam shape pattern and composite bore diameter structure, be conducive to the mass transfer in catalytic process, so as to accelerate
Rate of catalysis reaction.The composite bore diameter structure refers to both include the micropore that aperture is less than 2nm, again including aperture in 2nm-50nm
Between it is mesoporous, in addition to aperture be more than 50nm macropore.Step 1) in also include to it is obtained contain add and make in aluminum water solution
Hole agent, the molar concentration that the amount that the pore creating material is added to add pore creating material in rear solution is aluminum ions molar concentration
0.01-5 times.The pore creating material is cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), polyethylene
One or more in alcohol (PVA), polyethylene glycol (PEG) and calgon.CN101863499A
(201010187094.X) provides a kind of preparation method of macroporous-mesoporous alumina.Comprise the following steps：A. first reaction is helped
Agent and aluminium salt are dissolved in organic solvent solution, reaction promoter：Two kinds of material mol ratios of aluminium ion are 3-5：1, then by template
Add above-mentioned solution and dissolve, aluminium ion is 1 with template mol ratio：0.015-0.025, the pH value control of final solution exists
3.5-6.0；B., a is walked to the solution prepared and carries out burin-in process, making it, progressively organic solvent and moisture are obtained greatly in removing system
Hole-meso-porous alumina presoma；C. macroporous-mesoporous alumina powder is obtained through 400-800 DEG C of calcination process.Present invention process letter
Single, duct rule, pore-size distribution is concentrated and controllable adjustment can be realized according to concrete application situation, thus many in petrochemical industry
Mutually catalysis, adsorbing separation and as having important application value in terms of catalyst carrier, energy and material.Make full use of anti-
The space frame effect and coordination of auxiliary agent and template, and intermediary's organic polymer, reaction promoter are answered to inorganic ions
Complexing so that a step prepares the adjustable macroporous-mesoporous alumina material in aperture.Prepared foramen magnum-mesoporous oxidation
The specific surface area of aluminum is up to 250-320m2/ g, duct rule, pore-size distribution in mesoporous 5-40nm, macropore 50-150nm, and
It can be realized and adjusted according to actual conditions.Reaction promoter is organic acid, and aluminium salt is inorganic aluminate.Template is triblock copolymer.
Organic solvent is anhydrous alcohols, ethers or ketones solvent.Organic acid is citric acid or laurate.Triblock copolymer is
P123 or F127.(Langmuir, 2004,20 such as Tie-Zhen Ren：1531-1534) use nonionic surfactant
The aluminium secondary butylates of Brij 56 in acid condition use hydro-thermal method and Microwave-assisted synthesis macroporous-mesoporous alumina, synthesis it is porous
0.8-2 μm of alumina powder macropore diameter, mesoporous pore size 5-8nm, the aluminum oxide of 0.4-1.4 μm of hole wall.Its deficiency is aluminium-alcohol salt
Expensive, the macroporous-mesoporous alumina pore volume of synthesis is small, duct is irregular, pore-size distribution is excessive and can not realize pore structure
Effective regulation, thus, have significant limitation in using effect and scope.Jean-Philippe Dacquin etc.
(J.Am.Chem.Soc., 2009,131：12896-12897) use sol-gel process using P123 be template in mixed solution
It is middle to be introduced into the polystyrene droplet with single dispersed phase to realize the formation of macropore in macroporous-mesoporous alumina.Deficiency
Place is that macropore diameter size (300nm or 400nm) is determined by the size of secondary introducing polystyrene drop completely, i.e. macropore diameter
Size depends on polystyrene droplet size.Organic molecule in the part change to solution itself component and system can not be passed through
Interact to realize the adjustment in aperture.(the Inorganic Chemistry, 2009,48 such as Huining Li：4421) equally adopt
The polymethyl methacrylate with single dispersed phase is introduced in mixed solution by template of F127 with sol-gel process
(PMMA) droplet realizes the formation of macropore in macroporous-mesoporous alumina, weak point be macropore diameter size also completely by
Secondary introducing polymethyl methacrylate droplet size is determined, it is impossible to changed by the part to solution system itself component come real
Show the adjustment in aperture to realize the formation of foramen magnum-mesoporous composite pore structural, thus can not also realize the controllable of foramen magnum-mesoporous aperture
Regulation, in use, in particular for during the bulky molecular catalysis of complicated ingredient by significant limitation.
Above composite holes alumina support is typically used as mould using organic polymer such as polyvinyl alcohol, polymethylacrylic acid etc.
Plate agent either expanding agent.So that the preparation of composite holes and macroporous aluminium oxide material exist template monomer have certain toxicity,
Template consumption is larger, prepare the problems such as cost is higher, preparation process is cumbersome.Meanwhile, also there is the discharge in roasting process
The problem of thing environmental pollution.Also there is the patent of the adding carbohydrate compound in polymer microballoon emulsion.
CN201310142454.8 discloses a kind of preparation method of alumina hollow ball, preparation chitosan-acetic acid-water-soluble
Liquid；By polystyrene spheres:Chitosan-acetic acid-aqueous solution is 5:1-10：1 mass ratio, by polystyrene spheres：Alpha-alumina
Body is 1:5-1:15 mass ratio takes each raw material；Polystyrene spheres and chitosan-acetic acid-aqueous solution are mixed, make polyphenyl
Ethene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；The polyphenyl second of chitosan-acetic acid-aqueous solution is coated with again
Alkene ball is put into ball mill device with alpha-alumina powder, with 5-30r/s rotating speed rotation cladding 2-24h, and core-shell structure copolymer ball is made；Will
After the calcining of core-shell structure copolymer ball warp, that is, the alumina hollow ball that a diameter of 0.2-2mm, wall thickness are 20-100 μm is made.
CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional ordered macroporous oxidation
Aluminium, diameter macropores are 50-1000nm, and grain diameter is 1-50mm, and mechanical strength is 80-280g/mm.This method includes following step
Suddenly：Will into monodisperse polymer micro-sphere emulsion adding carbohydrate compound and the concentrated sulfuric acid, obtain the brilliant mould of polymer-modified microballoon glue
Plate, is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.The polymer microballoon
A diameter of 50-1000nm, can using polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and
One or more in the different monooctyl ester microballoon of polyacrylic acid, preferably polystyrene microsphere.Described single dispersing refers to polymer microballoon
The standard deviation of diameter is not more than 10%.The carbohydrate organic matter is the one or more in Soluble Monosaccharide and polysaccharide, preferably
For the one or more in sucrose, glucose, chitosan.This method can increase substantially the adhesion amount of aluminum oxide precursor, increase
The strong mechanical strength of material, it is trickle powder that when removing template is removed in high-temperature roasting, large pore material is not easily broken, can still be protected
Hold higher integrity degree.Chitosan is in ceramic coating sorbing material field using more.《Mesoporous chitosan-aluminium hydroxide is combined
Material Study on adsorption properties》(author：Peng Shaohua] University Of Suzhou,《Suzhou Institute of Science and Technology journal：Natural science edition》2013 30
Rolled up for 4 phases)：With chitosan and AlCl3For raw material, chitosan and α-Al (OH) are prepared for3Composite.With X-ray powder diffraction,
Transmission electron microscope, infrared, thermogravimetric and specific surface instrument have carried out sign results to it and shown：α-Al(OH)3It is in chitosan complexes
Existing typical mesoporous characteristic, BET specific surface area is 55.4m2g-1, BJH average pore sizes are 3.3nm；Specifically preparation method is：Claim
Take 2.0g Aluminium chloride hexahydrates to be dissolved in the hydrochloric acid that 5.0mL pH value is 1, add 2.0g chitosans, then add 10.0m L distillations
Water is stirred, and adjusts the pH value of solution to 1 with watery hydrochloric acid.Still aging 30min (solution becomes pasty state), is 14 with pH value
The pH value of NaOH solution regulation solution has white flock precipitate generation, suction filtration washes away the NaOH of residual with distilled water, is put into 8
Baking oven, product is obtained after being incubated 5h at 120 DEG C.As above step, it is respectively 1 that chitosan and aluminium chloride mass ratio are prepared respectively:2、1:
3、2:1、3:1 product.
《The preparation of chitosan/oxidized aluminium composite aerogel and sign》(Chang Xinhong；The chemicalization engineering of Luoyang Normal College
Institute,《Luoyang Normal College's journal》, 11 phases of volume 31 in 2012)：With chitosan and inorganic aluminate AlCl3.6H2O is raw material, is passed through
Sol-gel process, uses CO respectively2Supercritical drying means and freeze-drying means are prepared for new chitosan/oxidized aluminium
Composite aerogel.As a result show, the property such as specific surface area and pore volume of the content influence composite aerogel of chitosan, with shell
The increase of glycan content, the specific surface area of mixing aeroge is gradually reduced.Ratio table of the different drying means to composite aerogel
The properties such as area also have obvious influence.Composite aerogel contains micropore and mesoporous.CN201110022814.1 one kind has super
The ordered mesoporous metal oxide material of large aperture, it is characterised in that utilize the amphipathic block with ultrahigh molecular weight hydrophobic section
Copolymer is as structure directing agent, according to the principle of part assisted self assembling, before mesoporous material is made during solvent volatilizees
Drive and acted between body and structure directing agent, and microphase-separated is differently formed according to hydrophilic and hydrophobic, ultimately form to be situated between in order and see knot
Structure；Remove again after structure directing agent, form the ordered mesoporous metal oxide material with ultra-large aperture；Wherein, block copolymerization
The molecular weight of the hydrophobic block of thing is more than 10000g/mol；The ordered mesoporous metal oxide material mesoporous pore size is in 10-50nm
Between, mesoporous wall thickness of material is between 4-20nm.The hydrophilic block of the block copolymer is polyoxyethylene blocks；Institute
The hydrophobic block for stating block copolymer is polystyrene or derivatives thereof, polyacrylate or derivatives thereof, polymethylacrylic acid
One kind of ester or derivatives thereof, PLA pole or derivative, or two or more polymer described above copolymer.The invention system
Standby is meso-porous alumina, and similar also has CN101153051A, CN1631796A, CN101134567A, CN101823706A,
CN101863499A.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth ball-aluminium oxide hydrotreating and urged
Agent and preparation method thereof, including following components：Peptizing agent, 0.5-4 parts by weight；Lubricant, 0.2-2 parts by weight；Dispersant,
0.2-3 parts by weight；Expanding agent, 0.3-4 parts by weight；Aluminium hydroxide, 100 parts by weight.Expanding agent is polyvinyl alcohol, polyacrylic acid
One kind or mixture in sodium, starch derivatives or carbon black.The invention, which with the addition of anion surfactant, reduces various help
Specific surface area increases 246m while agent composition addition2/ g, expanding agent Sodium Polyacrylate.Tooth spherical alumina described in the invention
Alumina supporter, due to the wherein various auxiliary agents such as group such as peptizing agent, expanding agent, dispersant, anion surfactant is greatly lowered
Point content, not only saved cost, it is also big with specific surface area, the advantages of high mechanical strength.The invention has used peptizing agent,
Lubricant, dispersant, the reagent such as expanding agent, obtained alumina support is unimodal pore size distribution.CN201110116418.5 is carried
A kind of mesoporous sphere aluminum oxide is supplied and the method for preparing the mesoporous sphere aluminum oxide is oriented to using template.Using oil column into
Type method, is adding the template with guide function, Alumina gel is in shaping and aging into Alumina gel during preparing Alumina gel
During, because the presence of the template with guide function makes to produce substantial amounts of meso-hole structure in alumina balls.Template
For organic monomer or linear polymer, organic monomer is one kind in acrylic acid, ammonium acrylate, acrylamide, allyl alcohol.Jie
Hole spherical alumina aluminum ratio surface is 150-300m2/ g, particle diameter 0.1-5mm, pore volume is 0.7-1.5ml/g, and bore dia is
2-40nm hole is more than 97%, and heap density is 0.30-0.80g/cm3, crushing strength is 70-250N/.The invention utilizes template
Mesoporous sphere alumina pore diameter prepared by agent compares concentration, and this kind of mesoporous sphere aluminum oxide can be used for petrochemical industry and become more meticulous
Work as catalyst or catalyst carrier.
Macroporous aluminium oxide and compound porous aluminum oxide have different journeys to activity, selectivity and the stability aspect of catalyst
The improvement result of degree.Solubility of the polyvinyl alcohol template in water is influenceed by the degree of polymerization, causes it to be used for super big hole oxygen
Also it is subject to certain restrictions in the preparation for changing aluminium.
Prior art is mainly change support chemistry composition and type, and addition coagent to lift catalyst performance
Energy.Influence due to mercaptan to oil product product quality is maximum, and not only with foul smell, very strong corrosivity can also influence
The stability of product.Therefore needing mercaptan-eliminating catalyst to have, catalyst desulfurizing alcohol activity is high, and diolefin hydrogenation selectivity is high, pungent
Alkane value loses low characteristic.
The content of the invention
The problem to be solved in the present invention is to provide a kind of FCC gasoline mercaptan-eliminating catalyst, and the catalyst has removal of mercaptans work
Property it is high, diolefin hydrogenation selectivity is high, the characteristics of loss of octane number is low.Catalyst is using aluminum oxide as carrier, and alumina support is adopted
With chitosan as expanding agent, synthesize the alumina support with macroporous structure.Macroporous aluminium oxide has pore size adjustable
Section, the characteristics of macropore ratio can be controlled effectively.
The present invention provides a kind of for FCC gasoline mercaptan-eliminating catalyst, and the catalyst includes the oxidation with macroporous structure
Alumina supporter and the metal active constituent nickel and molybdenum being carried on carrier, by weight percentage, the aluminum oxide with macroporous structure
Carrier is 66-91wt%, and alumina support as expanding agent, contains adjuvant component phosphorus and magnesium, auxiliary agent using chitosan in carrier
The content of component phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality2O50.1-2.5wt%, MgO 0.1-2.5wt%, hole
Footpath is distributed 60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, pore volume 0.8-2.0ml/g, preferably
0.8-1.3ml/g or preferred 1.6-2.0ml/g, specific surface area 250-300m2/g.Nickel oxide content is 5-19wt%, molybdenum oxide
Content is 2-15wt%.
Preferably, adjuvant component cerium, adjuvant component cerium oxide are also contained in the alumina support with macroporous structure
Content account for carrier quality percentage composition be 0.1-2.5wt%.
Preferably, by weight percentage, the alumina support with macroporous structure is 71-88wt% to the catalyst,
Nickel oxide content is 6-17wt%.Oxidation molybdenum content is 5-12wt%.
The mercaptan-eliminating catalyst preparation method comprises the following steps：Soluble-salt containing cobalt and containing molybdenum is made into dipping
Liquid, alumina support of the dipping with macroporous structure, roasting 5-9 is small at being dried 4-8 hours, 650-800 DEG C at 120-160 DEG C
When, obtain mercaptan-eliminating catalyst.
The present invention has the alumina support of macroporous structure, and aperture can be by changing addition and the reaming of expanding agent
The molecular size range of agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-160nm,
The scopes such as 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, 35-50%, the scope such as 55-75%.
The present invention also provides a kind of preparation method of the alumina support with macroporous structure, first, is acidified with acid solution
Boehmite and sesbania powder, are then added in kneader and are well mixed by chitosan, add phosphoric acid, magnesium nitrate and mix molten
The acid solution of chitosan-containing, is finally added in boehmite and mediates uniform, the addition of the acid solution containing expanding agent by liquid
For the 0.1-8wt% of boehmite, preferably 0.2-5.0wt%, by extrusion-shaping-drying-roasting, obtain with macropore
The alumina support of structure.
The preparation method of alumina support with macroporous structure may be incorporated into cerium, such as by cerous nitrate and magnesium nitrate one
Play mixing to add in carrier, obtain the alumina support of phosphorous, magnesium, cerium.
The process of the acid solution acidified chitosan is as follows：First by chitosan expanding agent be added to 30-95 DEG C go from
In sub- water, acid is added dropwise afterwards, until chitosan dissolving is complete, the acid solution containing expanding agent is obtained.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The addition of acid is advisable with that can be completely dissolved chitosan.Also may be used
To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best
With ultrasonic oscillation or magnetic agitation.More than ultrasonic oscillation 10min, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Ripple shakes or magnetic agitation, and expanding agent good dispersion, alumina support is more prone to macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.The addition of the sesbania powder is the 0.1-7wt% of boehmite.
Extrusion technique is that the acid solution containing expanding agent configured is added in sesbania powder and boehmite and mixes equal
Even, extrusion, shaping afterwards is dried 3-9 hours, 650-800 DEG C is calcined 4-8 hours, finally gives with big by 100-160 DEG C
The alumina support of pore structure.
Alumina support of the present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure, simultaneously
Also contain meso-hole structure, macropore range is in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%, be a kind of containing Jie-macropore
Alumina support.And the not homogeneous aperture structure in aperture.
The alumina support with macroporous structure obtained using preparation method of the present invention, can also utilize phosphorus and magnesium
Carrier surface is modified, the concentration of phosphorus and magnesium is unsuitable too high, and preferably configuration concentration is less than phosphorus when preparing complex carrier
Acid and magnesium nitrate aqueous solution spray carrier surface, and carrier surface modification is preferably carried out as follows：Configure phosphoric acid and nitre
Alumina support of the aqueous solution spray with macroporous structure of sour magnesium, obtains used additives phosphorus through drying, roasting and magnesium carries out surface
Phosphorus pentoxide and content of magnesia are in 0.1- in modified alumina support, alumina support of the control with macroporous structure
In the range of 2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is set to be internal phosphorus pentoxide and magnesia
1.1-1.6 times of content.
The above-mentioned alumina support containing adjuvant component phosphorus, magnesium and cerium, can also be entered using phosphorus, magnesium and cerium to carrier surface
Row is modified, the aqueous solution spray carrier surface of configuration phosphoric acid, magnesium nitrate and cerous nitrate, and carrier is preferably carried out as follows
Surface is modified：Alumina support of the aqueous solution spray with macroporous structure of phosphoric acid, magnesium nitrate and cerous nitrate is configured, through dry
Dry, roasting obtains the alumina support that used additives phosphorus, magnesium and cerium carry out surface modification, carrying alumina of the control with macroporous structure
The content of phosphorus pentoxide, magnesia and cerium oxide is all in the range of 0.1-2.5wt% in body, and makes the oxidation of carrier surface five
The content of two phosphorus, magnesia and cerium oxide is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
Compared with prior art, the present invention has advantages below：
1st, catalyst carrier of the present invention is using chitosan as expanding agent, and expanding agent chitosan is cheap, and environmental protection
It is nontoxic, it is adapted to industrialized production.The obtained alumina support with macroporous structure, pore size can adjust, and macropore ratio can
Effectively to control.And carrier is also containing mesoporous, is a kind of Jie-macropore alumina supporter.Catalyst carrier has macroporous structure,
Catalyst is difficult coking and deactivation, and stability is good.
2nd, the present invention can also in alumina support and carrier surface introduce cerium, make carrier surface cerium content higher than load
Internal portion, should be prepared into mercaptan-eliminating catalyst with the alumina support of macroporous structure, and can suppress olefinic polymerization, and improve diene
Hydrogenation selectivity.
3rd, the alumina support with macroporous structure that the present invention is obtained, using phosphorus and magnesium or phosphorus, magnesium and cerium to big
The alumina carrier surface of pore structure is modified, and makes carrier surface phosphorus pentoxide, magnesia, the content of cerium oxide be interior
Portion's phosphorus pentoxide, magnesia, 1.1-1.6 times of cerium-oxide contents.Carrier surface is modified by the way of spray, energy
The partial pore of enough effective peptization carrier surfaces, so advantageously reduces the micropore ratio of carrier surface, improve carrier surface be situated between-
Macropore ratio, promotes carrier surface to produce more active sites load centres, improves removal of mercaptans activity.And in this carrier
Outer concentration of component different structure, makes alkadienes be not easily accessed inside duct and occurs polymerisation blocking duct.To carrier surface
Improvement should not use dipping method, impregnated carrier surface can make large quantity of moisture enter carrier, do not reach raising carrier surface be situated between-it is big
The purpose of boring ratio example.
4th, mercaptan-eliminating catalyst of the present invention be applied to removing liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/
Or mercaptan and/or alkadienes in coker gasoline；Or for being catalyzed diolefin selective hydrogenation.That is catalyst is to raw material
In alkene be not hydrogenated with, in the light hydrocarbons such as removing liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or coker gasoline
Mercaptan and/or alkadienes, catalyst choice are good.Octane number RON loss 0.3-0.4 points of gasoline or so.Catalyst desulfurizing alcohol
Active high, diolefin hydrogenation selectivity is high, and loss of octane number is low.
Brief description of the drawings
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as the limit to the present invention
System.
Primary raw material used in catalyst is prepared to originate：Source chemicals used in the present invention are commercially available prod.
Embodiment 1
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water first, acetic acid is added dropwise afterwards, until
Chitosan dissolving is complete, obtains the acid solution containing expanding agent.Phosphatase 11 .46g, magnesium nitrate 7.35g are weighed respectively, by phosphoric acid and nitre
Sour magnesium, which is dissolved completely in 70g distilled water, is made into phosphorous, magnesium the aqueous solution.Weigh 350g boehmite powder and 20.0g fields
Cyanines powder is added in kneader, and is well mixed, and adds the mixed solution of phosphoric acid and magnesium nitrate, finally by the acid of chitosan-containing
Solution, which is added in boehmite, to be mediated uniformly, is clover shape by kneading-extruded moulding.It is small that 8 are dried at 120 DEG C
When, 700 DEG C are calcined 4 hours, obtain phosphorous and magnesium alumina support 1.Phosphorus pentoxide 0.5wt%, magnesia in carrier 1
0.8wt%.Alumina support specific surface area with macroporous structure is shown in Table 1 with pore-size distribution.
Nickel nitrate and ammonium molybdate are made into maceration extract, adding ammoniacal liquor regulation pH value carries oxide impregnation aluminium after salt whole dissolving
Body 1, is dried 6 hours, 680 DEG C are calcined 8 hours, obtain catalyst 1 at 130 DEG C.Catalyst 1 is mainly constituted：With macropore knot
The alumina support of structure is 79wt%, and nickel oxide content is 12wt%, and oxidation molybdenum content is 9wt%.
Embodiment 2
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water, acetic acid is added dropwise afterwards, until shell gathers
Sugar dissolving is complete, obtains the acid solution containing expanding agent.Phosphatase 11 .09g, magnesium nitrate 9.12g are weighed respectively, by phosphoric acid and magnesium nitrate
It is dissolved completely in 70g distilled water and is made into phosphorous, magnesium the aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powders
It is added in kneader, and is well mixed, add the mixed solution of phosphoric acid and magnesium nitrate, finally by the acid solution of chitosan-containing
It is added in boehmite and mediates uniformly, is clover shape by kneading-extruded moulding.8 hours, 700 are dried at 120 DEG C
DEG C roasting 4 hours, obtains phosphorous and magnesium alumina support 1.Recycle phosphorus and magnesium to be modified carrier surface, configure phosphorous
Alumina support 1 of the aqueous solution spray with macroporous structure of acid and magnesium nitrate, is dried 8 hours, 700 DEG C of roastings 4 are small through 120 DEG C
When obtain the content of the alumina support 2 that used additives phosphorus and magnesium carry out surface modification, carrier surface phosphorus pentoxide and magnesia
It is 1.2 times of internal phosphorus pentoxide and content of magnesia.Alumina support specific surface area and aperture point with macroporous structure
Cloth is shown in Table 1.
Nickel nitrate and ammonium molybdate are made into maceration extract, adding ammoniacal liquor regulation pH value carries oxide impregnation aluminium after salt whole dissolving
Body 2, is dried 6 hours, 720 DEG C are calcined 5 hours, obtain catalyst 2 at 130 DEG C.Catalyst 2 is mainly constituted：With macropore knot
The alumina support of structure is 79.5wt%, and nickel oxide content is 10.5wt%, and oxidation molybdenum content is 10wt%.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.Difference is in carrier that adjuvant component also contains cerium, by water
Soluble chitosan expanding agent is replaced by water-insoluble chitosan expanding agent, 30 points of magnetic stirrer of chitosan formic acid liquid
Clock, obtains the alumina support 3 with macroporous structure.The content of adjuvant component phosphorus, magnesium and cerium accounts for the hundred of carrier quality in carrier
Point content is respectively 1.8wt%, 2.0wt%, 0.6wt%.Its specific surface area is shown in Table 1 with pore-size distribution.
Nickel nitrate and ammonium molybdate are made into maceration extract, adding ammoniacal liquor regulation pH value carries oxide impregnation aluminium after salt whole dissolving
Body 3, is dried 6 hours, 750 DEG C are calcined 5 hours, obtain catalyst 3 at 130 DEG C.Catalyst 3 is mainly constituted：With macropore knot
The alumina support of structure is 81.5wt%, and nickel oxide content is 6wt%, and oxidation molybdenum content is 12.5wt%.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 3.Difference is water soluble chitosan expanding agent being replaced by
Water-insoluble chitosan expanding agent, chitosan acetic acid solution ultrasonic oscillation 15 minutes.Obtain the aluminum oxide with macroporous structure
Carrier.The percentage composition that the content of adjuvant component phosphorus, magnesium and cerium accounts for carrier quality in carrier be respectively 1.6wt%, 1.6wt%,
0.6wt%.Recycle phosphorus, magnesium and cerium to be modified carrier surface, obtain carrier 4, the surface phosphorus pentoxide of carrier 4, oxidation
The content of cerium and magnesia is 1.5 times of internal phosphorus pentoxide, cerium oxide and content of magnesia.Oxidation with macroporous structure
The specific surface area of alumina supporter 4 is shown in Table 1 with pore-size distribution.
Nickel nitrate and ammonium molybdate are made into maceration extract, adding ammoniacal liquor regulation pH value carries oxide impregnation aluminium after salt whole dissolving
Body 4, is dried 6 hours, 750 DEG C are calcined 5 hours, obtain catalyst 4 at 130 DEG C.Catalyst 4 is mainly constituted：With macropore knot
The alumina support of structure is 77.5wt%, and nickel oxide content is 16wt%, and oxidation molybdenum content is 6.5wt%.
Embodiment 5
The preparation method of carrier is carried out according to embodiment 2, except that carrier surface phosphorus pentoxide and magnesia
Content is 1.4 times of internal phosphorus pentoxide and content of magnesia.Catalyst 5 is mainly constituted：Aluminum oxide with macroporous structure
Carrier is 80.5wt%, and nickel oxide content is 5.5wt%, and oxidation molybdenum content is 14wt%.
Embodiment 6
The preparation method of carrier is carried out according to embodiment 4, except that surface phosphorus pentoxide, cerium oxide and magnesia
Content be 1.3 times of internal phosphorus pentoxide, cerium oxide and content of magnesia.Catalyst 6 is mainly constituted：With macroporous structure
Alumina support be 78wt%, nickel oxide content is 13.5wt%, oxidation molybdenum content be 8.5wt%.
The alumina support specific surface area and pore-size distribution of the macropore of table 1
Catalyst 1-4 is loaded into fixed bed reactors respectively, carries out evaluating catalyst reaction performance.With sulfurized oil pair
Catalyst carries out presulfurization, and sulfide stress is 3.2MPa, and hydrogen to oil volume ratio is 300, and sulfurized oil volume space velocity is 3.5h-1, vulcanization
Program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After vulcanizing treatment terminates, switch at full cut FCC gasoline displacement
6h is managed, reaction process condition is then adjusted to, sweetening reaction is carried out.FCC feedstock content of sulfur in gasoline 556 μ g/g, the μ of mercaptan sulfur 35
G/g, olefin(e) centent 47.35v%, RON 88.36.Reaction process condition is：115 DEG C of temperature of reactor, volume space velocity 3.3h-1,
Hydrogen to oil volume ratio 11:1, reaction pressure 2.1MPa.React sampling analysis after about 55h.Catalyst 1-4 reaction results are as follows：Catalysis
The μ g/g of 1 sulfur content of agent 544, mercaptan sulfur 5 μ g/g, olefin(e) centent 46.59v%, RON 87.93, yield of gasoline 97.8wt%；Catalysis
The μ g/g of 2 sulfur content of agent 547, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.83v%, RON 87.95, yield of gasoline 98.2wt%；Catalysis
The μ g/g of 3 sulfur content of agent 545, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.85v%, RON 88.01, yield of gasoline 98.0wt%；Catalysis
The μ g/g of 4 sulfur content of agent 548, mercaptan sulfur 2 μ g/g, olefin(e) centent 46.82v%, RON 88.03, yield of gasoline 98.5wt%；Catalysis
Agent product mercaptan sulfur is less than 4 μ g/g, and olefin(e) centent is basically unchanged, and reaction loss of octane number is in 0.3-0.4, and catalyst activity is high,
Selectivity is good, and loss of octane number is low.Stability test, reaction operation 400h, the μ g/ of 1 sulfur content of catalyst 542 are carried out to catalyst
G, mercaptan sulfur 4 μ g/g, olefin(e) centent 46.56v%, RON 7.91, yield of gasoline 97.9wt%；The μ g/ of 2 sulfur content of catalyst 546
G, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.82v%, RON 7.94, yield of gasoline 98.0wt%；The μ g/ of 3 sulfur content of catalyst 545
G, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.84v%, RON 7.98, yield of gasoline 98.1wt%；The μ g/ of 4 sulfur content of catalyst 547
G, mercaptan sulfur 2 μ g/g, olefin(e) centent 46.83v%, RON 8.04, yield of gasoline 98.4wt%；Product after catalyst operation 400h
Mercaptan sulfur is less than 4 μ g/g, and olefin(e) centent is basically unchanged, and catalyst is difficult coking and deactivation, and stability is good.
Catalyst 5-6 is loaded into fixed bed reactors respectively, carries out evaluating catalyst reaction performance.With sulfurized oil pair
Catalyst carries out presulfurization, and sulfide stress is 3.2MPa, and hydrogen to oil volume ratio is 300, and sulfurized oil volume space velocity is 3.5h-1, vulcanization
Program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After vulcanizing treatment terminates, switch at full cut FCC gasoline displacement
6h is managed, reaction process condition is then adjusted to, sweetening reaction is carried out.FCC feedstock content of sulfur in gasoline 733 μ g/g, the μ of mercaptan sulfur 28
G/g, olefin(e) centent 44.68v%, RON 9.24.Reaction process condition is：145 DEG C of temperature of reactor, volume space velocity 2.2h-1, hydrogen
Oil volume compares 14:1, reaction pressure 2.7MPa.React sampling analysis, 5 sulfur content of catalyst 724 μ g/g, the μ of mercaptan sulfur 2 after about 55h
G/g, olefin(e) centent 43.95v%, RON 8.95, yield of gasoline 98.3wt%；6 sulfur content of catalyst 725 μ g/g, the μ of mercaptan sulfur 2
G/g, olefin(e) centent 44.19v%, RON 9.01, yield of gasoline 98.6wt%.Catalyst activity is high, and selectivity is good, and octane number is damaged
Lose low, catalyst is to different sulfur contents, the oil product strong adaptability of mercaptan sulfur content and olefin(e) centent.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
Protection scope of the present invention should all be belonged to.
Claims (10)
1. a kind of catalyst for FCC gasoline removal of mercaptans, it is characterised in that：
Catalyst includes the alumina support with macroporous structure and the metal active constituent nickel and molybdenum that are carried on carrier, with weight
Percentages are measured, the alumina support with macroporous structure is 66-91wt%, and alumina support is used as reaming using chitosan
Containing adjuvant component phosphorus and magnesium in agent, carrier, the content of adjuvant component phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality2O5
0.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-75%, pore volume 0.8-2.0ml/g,
Specific surface area 250-300m2/g；Nickel oxide content is 5-19wt%, and oxidation molybdenum content is 2-15wt%.
2. a kind of catalyst for FCC gasoline removal of mercaptans according to claim 1, it is characterised in that：The catalyst
By weight percentage, the alumina support with macroporous structure is 71-88wt%, and nickel oxide content is 6-17wt%.Oxidation
Molybdenum content is 5-12wt%.
3. a kind of a kind of preparation method of catalyst for FCC gasoline removal of mercaptans described in claim 1, it is characterised in that：
Comprise the following steps：Soluble-salt containing cobalt and containing molybdenum is made into maceration extract, dipping has the alumina support of macroporous structure,
It is calcined 5-9 hours at being dried 4-8 hours, 650-800 DEG C at 120-160 DEG C, obtains mercaptan-eliminating catalyst.
4. a kind of catalyst for FCC gasoline removal of mercaptans according to claim 1, it is characterised in that：It is described to have greatly
Also contain adjuvant component cerium in the alumina support of pore structure, the content of adjuvant component cerium oxide accounts for the percentage composition of carrier quality
For 0.1-2.5wt%.
5. a kind of catalyst for FCC gasoline removal of mercaptans according to claim 1, it is characterised in that：It is described to have greatly
The preparation method of the alumina support of pore structure comprises the following steps：First, acid solution acidified chitosan is used, then will intend thin water
Aluminium stone and sesbania powder are added in kneader and are well mixed, and add the mixed solution of phosphoric acid and magnesium nitrate, will finally contain shell and gather
The acid solution of sugar, which is added in boehmite, to be mediated uniformly, and the addition of the acid solution containing expanding agent is boehmite
0.1-8wt%, by extrusion-shaping-drying-roasting, obtains the alumina support with macroporous structure.
6. a kind of catalyst for FCC gasoline removal of mercaptans according to claim 1, it is characterised in that：The aluminum oxide
Carrier also contains meso-hole structure simultaneously, and macropore range is in 5-50nm, mesoporous ratio 15-75%.
7. a kind of catalyst for FCC gasoline removal of mercaptans according to claim 4, it is characterised in that：It is described to have greatly
The preparation method of the alumina support of pore structure comprises the following steps：First, acid solution acidified chitosan is used, then will intend thin water
Aluminium stone and sesbania powder are added in kneader and are well mixed, and add the mixed solution of phosphoric acid, magnesium nitrate and cerous nitrate, finally will
The acid solution of chitosan-containing, which is added in boehmite, to be mediated uniformly, and the addition of the acid solution containing expanding agent is the thin water aluminium of plan
The 0.1-8wt% of stone, by extrusion-shaping-drying-roasting, obtains the alumina support with macroporous structure.
8. a kind of catalyst for FCC gasoline removal of mercaptans according to claim 7, it is characterised in that：To claim 7
The obtained alumina support with macroporous structure, is modified using phosphorus, magnesium and cerium to carrier surface：Configure phosphoric acid, nitre
Sour magnesium and cerous nitrate the aqueous solution spray with macroporous structure alumina support, through drying, roasting obtain used additives phosphorus, magnesium and
Cerium carry out surface modification alumina support, control with macroporous structure alumina support in phosphorus pentoxide, magnesia and
The content of cerium oxide makes containing for carrier surface phosphorus pentoxide, magnesia and cerium oxide all in the range of 0.1-2.5wt%
Amount is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
9. a kind of catalyst for FCC gasoline removal of mercaptans according to claim 5, it is characterised in that：To claim 5
The obtained alumina support with macroporous structure, is modified using phosphorus and magnesium to carrier surface：Configure phosphoric acid and nitric acid
Alumina support of the aqueous solution spray with macroporous structure of magnesium, obtains used additives phosphorus through drying, roasting and magnesium carries out surface and changed
Property alumina support, phosphorus pentoxide and content of magnesia are respectively in 0.1- in alumina support of the control with macroporous structure
In the range of 2.5wt% and 0.1-2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is set to be internal five oxidation
1.1-1.6 times of two phosphorus and content of magnesia.
10. a kind of catalyst for FCC gasoline removal of mercaptans according to claim 5, it is characterised in that：The acid solution
The process of acidified chitosan is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, acid is added dropwise afterwards,
Until chitosan dissolving is complete, the acid solution containing expanding agent is obtained.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364966A (en) * | 2018-10-14 | 2019-02-22 | 黄志祥 | A kind of catalyst and preparation method of demercaptaning for gasoline |
| CN109423324A (en) * | 2017-08-31 | 2019-03-05 | 中国石油天然气股份有限公司 | A kind of method of FCC gasoline removal of mercaptans |
| CN109420506A (en) * | 2017-08-31 | 2019-03-05 | 中国石油天然气股份有限公司 | A kind of catalyst and preparation method of demercaptaning for gasoline |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609171A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and its prepn process |
| CN101433841A (en) * | 2007-12-13 | 2009-05-20 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
| CN101863499A (en) * | 2010-05-31 | 2010-10-20 | 中南大学 | Preparation method of macroporous-mesoporous alumina |
| CN102451694A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation dethiolizing catalyst, preparation method thereof and application thereof |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
-
2017
- 2017-06-02 CN CN201710412089.6A patent/CN107096552B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609171A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and its prepn process |
| CN101433841A (en) * | 2007-12-13 | 2009-05-20 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
| CN101863499A (en) * | 2010-05-31 | 2010-10-20 | 中南大学 | Preparation method of macroporous-mesoporous alumina |
| CN102451694A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation dethiolizing catalyst, preparation method thereof and application thereof |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109420506A (en) * | 2017-08-31 | 2019-03-05 | 中国石油天然气股份有限公司 | A kind of catalyst and preparation method of demercaptaning for gasoline |
| CN109420506B (en) * | 2017-08-31 | 2021-07-30 | 中国石油天然气股份有限公司 | Catalyst for removing mercaptan from gasoline and preparation method thereof |
| CN109897663B (en) * | 2017-12-07 | 2021-07-02 | 中国石油天然气股份有限公司 | FCC gasoline desulfurization treatment method |
| CN109894122A (en) * | 2017-12-07 | 2019-06-18 | 中国石油天然气股份有限公司 | A kind of FCC gasoline Hydrobon catalyst and preparation method thereof |
| CN109894122B (en) * | 2017-12-07 | 2021-06-01 | 中国石油天然气股份有限公司 | FCC gasoline hydrodesulfurization catalyst and preparation method thereof |
| CN109897663A (en) * | 2017-12-07 | 2019-06-18 | 中国石油天然气股份有限公司 | A kind of processing method of FCC gasoline desulfurization |
| CN109364966A (en) * | 2018-10-14 | 2019-02-22 | 黄志祥 | A kind of catalyst and preparation method of demercaptaning for gasoline |
| CN109364966B (en) * | 2018-10-14 | 2021-10-29 | 上海光华供应链管理有限公司 | Catalyst for removing mercaptan from gasoline and preparation method thereof |
| CN110201637A (en) * | 2019-06-13 | 2019-09-06 | 中国石油大学(华东) | A kind of preparation method for organic sulfur compound removing adsorbent in natural gas |
| CN110201637B (en) * | 2019-06-13 | 2021-11-26 | 中石化中原石油工程设计有限公司 | Preparation method of adsorbent for removing organic sulfide in natural gas |
| CN114433108A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst with core-shell structure |
| CN114433108B (en) * | 2020-10-31 | 2023-10-10 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst with core-shell structure |
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