CN106902878A - It is a kind of for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation and preparation method thereof - Google Patents
It is a kind of for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation and preparation method thereof Download PDFInfo
- Publication number
- CN106902878A CN106902878A CN201710049488.0A CN201710049488A CN106902878A CN 106902878 A CN106902878 A CN 106902878A CN 201710049488 A CN201710049488 A CN 201710049488A CN 106902878 A CN106902878 A CN 106902878A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- desulfurization
- gasoline
- coal tar
- denitrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 20
- 230000023556 desulfurization Effects 0.000 title claims abstract description 20
- 239000011280 coal tar Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 239000011149 active material Substances 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004480 active ingredient Substances 0.000 claims abstract description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000011964 heteropoly acid Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 244000215068 Acacia senegal Species 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229920003086 cellulose ether Polymers 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 claims description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- -1 hydroxypropyl methyl Chemical group 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000011686 zinc sulphate Substances 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000009940 knitting Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000027950 fever generation Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940009493 gel-one Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- 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
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—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
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of for gasoline, coal tar hydrorefining desulfurization, denitrification catalyst and preparation method thereof, including catalyst carrier and carrier loaded active material, through hole centered on described catalyst, 1~2mm of diameter it is cylindric, its voidage is 1.2~1.6 times of the real core catalyst carrier of same equivalent diameter, and active component is 0.2~0.5 times of the other structures catalyst of same equivalent diameter；The material of described catalyst carrier includes the mixture or the mixture of aluminum oxide series material and titanium oxide series material of aluminum oxide series material or aluminum oxide series material and silica series material, the active material of load contains cobalt, nickel, molybdenum, zinc, one or more in phosphorus.The voidage of the catalyst is 1.2~1.6 times of the real core catalyst carrier of same equivalent diameter, and the amount of active ingredients for being used is also 50~80% of other catalyst under same volume, and the usage amount of catalyst activity component is greatly saved, and has saved resource.
Description
Technical field
Field is manufactured the present invention relates to the catalyst used by oil refining industry, is specifically related to a kind of for gasoline, coal
Hydrogenation of tar refining desulfurization, catalyst of denitrogenation and preparation method thereof.
Background technology
Also more and more strong to asking for for natural resources with the progress of human civilization, the destruction to environment is also increasingly serious,
And most of resources be it is limited, it is non-renewable, therefore meet permanently effective utilization and conservation of nature ring of the mankind to resource
Border is the very urgent responsibilities and obligations of owner.We must accomplish to increase income and decrease expenditure, and take exploitation new technology, improve resource profit
With measures such as rates, it is intended to economize on resources and be reduced or avoided the destruction to environment, Blue Sky is left to descendants.
And oil refining industry be natural resources exploitation using and environmental pollution than more serious industry；Use is urged more at present
Agent carries out the removing of pollutant, to weaken the pollution to environment；Particularly it is used for gasoline, coal tar hydrorefining desulfurization, takes off
The catalyst of nitrogen, the composition of such catalyst mainly includes carrier and active material, and it is straight that carrier structure therein is mainly equivalent
The bar shaped reality core body of 0.5~3mm of footpath, such as " clover " type, cylindrical type etc., the catalyst carrier technology of the series structure into
It is ripe, industrialize for many years, there is its advantage, also there is its inferior position, advantage is technology maturation, simple production process；Inferior position is manufacture
Catalyst buildup voidage is small, with the catalyst under the conditions of equivalent responses, required more active components.
The content of the invention
Above-mentioned deficiency of the present invention for prior art, there is provided one kind is used for gasoline, coal tar hydrorefining desulfurization, denitrogenation
Catalyst, the voidage of the catalyst is 1.2~1.6 times of the real core catalyst carrier of same equivalent diameter, the work for being used
Property group component is also 50~80% of other catalyst under same volume, and the use of catalyst activity component is greatly saved
Amount, has saved resource.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：One kind is for gasoline, coal tar hydrogenating essence
Desulfurization processed, denitrification catalyst, including catalyst carrier and carrier loaded active material, through hole centered on described catalyst,
1~2mm's of diameter is cylindric, and its voidage is 1.2~1.6 times of the real core catalyst carrier of same equivalent diameter, active component
It is 0.2~0.5 times of the other structures catalyst of same equivalent diameter；The material of described catalyst carrier includes aluminum oxide series
The mixture or aluminum oxide series material and titanium oxide series material of material or aluminum oxide series material and silica series material
The mixture of material, the active material of load contain one kind in cobalt (Co), nickel (Ni), molybdenum (Mo), zinc (Zn), phosphorus (P) etc. or
It is various.
Described aluminum oxide series material includes but is not limited to the one of the aluminum oxide series material such as boehmite, Alumina gel
Plant or various powders for mixing composition.
Described silica series material is referred to but is not limited to Ludox, and aerosil etc. is mixed for one or more
The material being combined into.
The present invention also provide it is a kind of it is above-mentioned for gasoline, coal tar hydrorefining desulfurization, denitrification catalyst preparation method,
Specific step includes：
(1) it is 80~100 according to weight ratio by aluminum oxide and silica series material：0~20 ratio is made into mixing
Material, it is the 0.5~10% of compound weight to aid in binding agent, and it is the 35~70% of compound weight to add water, and peptizing agent is mixed
The 0.5~5% of material weight is closed, pug is mixed into；
(2) using Application No. 2016109656335, entitled《A kind of miniature catalyst carrier mould, the mould
Manufacture craft and method that carrier is prepared using the mould》Described mould, with reference to step (1) pug prepare it is a diameter of
The catalyst carrier base substrate of the rice-shaped of 1~2mm；
(3) billet of the 2~12mm of catalyst carrier base substrate cut-out growth for preparing step (2)；Then in room temperature~200
DEG C temperature environment under dry to base substrate moisture content no more than 5%；Finally by dried base substrate by kiln 450~
1000 DEG C of temperature calcinations 5~15 hours；
(4) the supported on carriers active ingredients substances obtained in step (3)：Prepare Ni-Mo-P-Zn's or Co-Mo-P-Zn
Presoma constitute active component heteropoly acid mixed solution, by isometric, saturation impregnating mode step (3) carrier
The above-mentioned heteropoly acid mixed solution of upper load；
(5) dried 5~30 hours at the catalyst that step (4) is obtained being positioned over into 50~200 DEG C；
(6) product for completing step (5) is calcined 5~35 hours by kiln at 350~750 DEG C, is completed catalyst and is produced
Product are manufactured.
Binding agent described in step (1) of the present invention is：Methylcellulose, cellulose ether, hydroxypropyl methyl fiber, plain hydroxyl second
One or more mixture in base cellulose, carboxymethylcellulose calcium, sesbania gum, gum arabic etc..
Peptizing agent described in step (1) of the present invention is the one kind in technical pure nitric acid, technical pure acetic acid, technical pure oxalic acid etc.
Or more than one.
Aluminum oxide series material described in step (1) of the present invention includes but is not limited to the oxidation such as boehmite, Alumina gel
One or more powder of mixing composition in aluminium series material.
Silica series material described in step (1) of the present invention is referred to but is not limited to Ludox, gas phase titanium dioxide
One or more material of mixing composition such as silicon.
Ni (nickel) presoma is the other nickel nitrate of catalyst grade, nickelous carbonate or basic carbonate in above-mentioned steps (4) of the present invention
Nickel；Mo (molybdenum) presoma is the other molybdenum oxide of catalyst grade, ammonium heptamolybdate or other molybdates；P (phosphorus) predecessor is net content
It is 85% phosphoric acid；Co (cobalt) presoma is the other cobalt nitrate of catalyst grade, cobalt carbonate or basic cobaltous carbonate；Zn is industrial-purity zinc
Salt is (such as：ZnCl2、ZnSO4、Zn(NO3)2、Zn(ClO4)2)。
The advantages of the present invention：
1. this method production catalyst void rate be equal equivalent diameter three leaves or bunge bedstraw herb shape catalyst 1.2~
1.6 times, big voidage can provide bigger external surface area to increase the contact frequency of catalyst and reactive material, improve reaction
Efficiency, by reaction complete material also can quickly escape with avoid local pyrexia make temperature of reactor rise and induction accident；
2. the use of this catalyst amount is its of same equivalent diameter in equal volume reactor in the case where use is ensured
0.5~0.8 times of the catalyst of its structure, i.e., this catalyst is loaded under same volume can save 20~50% catalyst amounts, section
About catalyst amount, cost-effective considerable；
3. using this technology produce catalyst consumed in active component be only same equivalent diameter other structures be catalyzed
0.2~0.5 times of agent, the economy and social effect for economizing on resources produced is considerable.This technology is used for gasoline, and coal tar adds
The chemical processing fields such as hydrogen desulfurization, denitrogenation, can be greatly saved resource, and the gasoline produced can meet the standard of state 5.
Brief description of the drawings
Mould generalized section in Fig. 1 Application No.s 2016109656335.
Formpiston in Fig. 2 Application No.s 2016109656335 overlooks figure structure schematic representation.
Former in Fig. 3 Application No.s 2016109656335 overlooks figure structure schematic representation.
Formpiston structural representation in Fig. 4 Application No.s 2016109656335.
Female mould structure schematic diagram in Fig. 5 Application No.s 2016109656335.
Specific embodiment
The present invention is described in further detail below by embodiment, but the present invention is not limited solely to following examples.
Embodiment
(1) boehmite original powder 1kg, methylcellulose 30g are taken, batch mixer batch mixing is put into the lump and is added water after 5 minutes
550g and 20g nitric acid, continues batch mixing until powder all becomes pug for this；
(2) in the pug input pressure extruder for completing step (1), by Application No. 2016109656335, invention
It is entitled《A kind of miniature catalyst carrier mould, the manufacture craft of the mould and the method that carrier is prepared using the mould》Middle institute
The mould extrusion molding stated；
Specifically, as shown in accompanying drawing 1-5, the miniature catalyst carrier mould in Application No. 2016109656335, the mould
Tool includes formpiston 1 and former 2, and described formpiston and one end of former are laminated；Described formpiston is axially disposed some
Enter mud hole 3 and large knitting needle accommodating hole 4, be plugged with described large knitting needle accommodating hole and lead mud rod 5；Described former is axially arranged some
Forming hole 6, when one end of formpiston and former is laminated, described forming hole and large knitting needle accommodating hole coaxial line and described
Mud rod is led through forming hole and large knitting needle accommodating hole；Described former axially inwardly sets fluted 7, institute with the end face of formpiston pressing
The groove stated forms interlayer gap 8 with the end face of formpiston；Internal diameter of the described external diameter for leading mud rod less than forming hole.Using above-mentioned
Structure, one end of formpiston and former is laminated, and then will be led mud rod and is inserted into forming hole from large knitting needle accommodating hole one end, and
Termination protrudes from forming hole；Then the catalyst carrier pug containing active material is entered by press from mud pore pressure is entered, is entered
Formed to groove and be sufficiently mixed in interlayer gap, then extruded from forming hole, obtain hollow catalyst carrier, this structure
Carrier is set due to boring, can cause that catalysis area becomes big, improves catalytic efficiency, reduces cost so that material use
Rate is more abundant.
(3) base substrate that step (2) is manufactured is put into 70 DEG C of baking ovens freeze-day with constant temperature 8 hours, is to base substrate moisture content
0.83%；
(4) base substrate for taking step (3) is calcined 6 hours for 580 DEG C with Muffle furnace；
(5) content according to each active component in table 1 in the catalyst, with nickel nitrate, molybdenum acid ammonia, zinc nitrate, phosphorus
Mixture of multi-elements liquid medicine is prepared in acid, and active component solution is impregnated by isometric method (equi-volume process)；It is specifically shown in table 1 below institute
Show：
Table 1 each active component content in the catalyst
| Project | Grain of rice ring catalyst activity content of material | Real core trifolium-shaped catalyst |
| 7 | 13 | |
| Co (%) | 0.8 | 1.5 |
| Zn (%) | 0.5 | 0.9 |
| Ni (%) | 0.2 | 0.2 |
| P (%) | 0.9 | 1.8 |
(6) product of step (5) is put to baking oven, after being dried 24 hours with 60 DEG C of temperature, then is placed in Muffle furnace
500 DEG C of temperature calcinations complete catalyst manufacture for 4 hours.
Under equal conditions, the catalyst and traditional trifolium-shaped carrier for being manufactured using this patent in unit volume use effect
Fruit contrast is shown in Table 2：
The embodiment of the present invention sample of table 2 and prior art sample comparative result
Knowable to above-mentioned contrast, there is catalyst of the invention big voidage can provide bigger external surface area to increase
Plus catalyst and the contact frequency of reactive material, reaction efficiency being improved, also quickly can escape to avoid by the material that reaction is completed
Local pyrexia makes temperature of reactor rise and induction accident；And compared with the other structures catalyst with equivalent diameter active matter
The consumption of matter is more saved, but desulfurization degree and denitrification percent are higher.
Claims (10)
1. it is a kind of for gasoline, coal tar hydrorefining desulfurization, denitrogenation catalyst, it is characterised in that：Including catalyst carrier
With carrier loaded active material, through hole centered on described catalyst, 1~2mm of diameter it is cylindric, its voidage is with working as
Measure the real core catalyst carrier of diameter 1.2~1.6 times, active component is the 0.2 of the other structures catalyst of same equivalent diameter
~0.5 times；The material of described catalyst carrier includes aluminum oxide series material or aluminum oxide series material and silica-based
The mixture of row material or the mixture of aluminum oxide series material and titanium oxide series material, the active material of load contain cobalt,
Nickel, molybdenum, zinc, one or more in phosphorus.
2. it is according to claim 1 for gasoline, coal tar hydrorefining desulfurization, denitrogenation catalyst, it is characterised in that：
Described aluminum oxide series material includes but is not limited to the mixing of one or more in boehmite, Alumina gel.
3. it is according to claim 1 for gasoline, coal tar hydrorefining desulfurization, denitrogenation catalyst, it is characterised in that：
Described silica series material includes but is not limited to Ludox, the mixing of one or more in aerosil.
4. it is a kind of for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation preparation method, it is characterised in that：Step
Including：
(1) it is 80~100 according to weight ratio by aluminum oxide and silica series material：0~20 ratio is made into compound, auxiliary
It is the 0.5~10% of compound weight to help binding agent, and it is the 35~70% of compound weight to add water, and peptizing agent is compound weight
The 0.5~5% of amount, mixes into pug；
(2) using Application No. 2016109656335, entitled《A kind of miniature catalyst carrier mould, the system of the mould
The method made technique and carrier is prepared using the mould》Described mould, with reference to step (1) pug prepare a diameter of 1~
The catalyst carrier base substrate of the rice-shaped of 2mm；
(3) billet of the 2~12mm of catalyst carrier base substrate cut-out growth for preparing step (2)；Then in room temperature~200 DEG C
Dried under temperature environment being no more than 5% to base substrate moisture content；Finally by dried base substrate by 450~1000 DEG C of kiln
Temperature calcination 5~15 hours；
(4) the supported on carriers active ingredients substances obtained in step (3)：The forerunner for preparing Ni-Mo-P-Zn or Co-Mo-P-Zn
The heteropoly acid mixed solution of the active component that body is constituted, is born by isometric, saturation impregnating mode on the carrier of step (3)
Carry above-mentioned heteropoly acid mixed solution；
(5) dried 5~30 hours at the catalyst that step (4) is obtained being positioned over into 50~200 DEG C；
(6) product for completing step (5) is calcined 5~35 hours by kiln at 350~750 DEG C, completes catalyst prod system
Make.
5. it is according to claim 4 for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation preparation method,
It is characterized in that：Binding agent described in step (1) is：Methylcellulose, cellulose ether, hydroxypropyl methyl fiber, plain ethoxy
Cellulose, carboxymethylcellulose calcium, one or more in sesbania gum, gum arabic of mixture.
6. it is according to claim 4 for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation preparation method,
It is characterized in that：Peptizing agent described in step (1) is the one kind or two in technical pure nitric acid, technical pure acetic acid, technical pure oxalic acid
More than kind.
7. it is according to claim 4 for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation preparation method,
It is characterized in that：Aluminum oxide series material described in step (1) include but is not limited to one kind in boehmite, Alumina gel or
Various mixing.
8. it is according to claim 4 for gasoline, coal tar hydrorefining desulfurization, denitrification catalyst preparation method, its
It is characterised by：Silica series material described in step (1) includes but is not limited to Ludox, the one kind in aerosil
Or various mixing.
9. it is according to claim 4 for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation preparation method,
It is characterized in that：Ni presomas are the other nickel nitrate of catalyst grade, nickelous carbonate or basic nickel carbonate in step (4)；Mo presomas
For the other molybdenum oxide of catalyst grade, ammonium heptamolybdate or other molybdates；P predecessors are phosphoric acid that net content is 85%；Co forerunner
Body is the other cobalt nitrate of catalyst grade, cobalt carbonate or basic cobaltous carbonate；Zn predecessors are technical pure zinc salt.
10. it is according to claim 9 for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation preparation method,
It is characterized in that：Described technical pure zinc salt is ZnCl2、ZnSO4、Zn(NO3)2、Zn(ClO4)2In one or two kinds of more than
Mixing.
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Cited By (3)
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| CN110756204A (en) * | 2019-10-24 | 2020-02-07 | 西安石油大学 | Preparation and catalysis method of catalyst for converting phenolic compounds in coal tar |
| CN113083270A (en) * | 2021-04-14 | 2021-07-09 | 江苏扬农化工集团有限公司 | Catalyst for synthesizing 6-aminocapronitrile from cyclohexanone oxime by one-step method and preparation method thereof |
| CN116422345A (en) * | 2023-05-17 | 2023-07-14 | 中国石油大学(北京) | A kind of titanium base hydrogenation catalyst and its preparation method and application |
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