CN107282053A - Suitable for the preparation method of the hydrogenation catalyst of high nitrogen-containing diesel oil - Google Patents
Suitable for the preparation method of the hydrogenation catalyst of high nitrogen-containing diesel oil Download PDFInfo
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- CN107282053A CN107282053A CN201710486276.9A CN201710486276A CN107282053A CN 107282053 A CN107282053 A CN 107282053A CN 201710486276 A CN201710486276 A CN 201710486276A CN 107282053 A CN107282053 A CN 107282053A
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- diesel oil
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- high nitrogen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 25
- 230000000996 additive effect Effects 0.000 claims abstract description 25
- 239000008139 complexing agent Substances 0.000 claims abstract description 24
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 22
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 90
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 46
- 229960004106 citric acid Drugs 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 239000004115 Sodium Silicate Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 20
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 20
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 15
- 229940070765 laurate Drugs 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000011975 tartaric acid Substances 0.000 claims description 15
- 235000002906 tartaric acid Nutrition 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 10
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 10
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 10
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 10
- 239000010687 lubricating oil Substances 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229940022682 acetone Drugs 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001404 mediated effect Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- PXDJXZJSCPSGGI-UHFFFAOYSA-N palmityl palmitate Chemical group CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 230000003111 delayed effect Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
- 230000023556 desulfurization Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003921 oil Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
-
- 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
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of the hydrogenation catalyst suitable for high nitrogen-containing diesel oil, including following preparation process：Aluminium hydroxide is prepared, carrier is prepared, prepares complexing agent, prepare additive, prepare catalyst and modification.The preparation method of the present invention is simple, the catalyst of preparation is using aluminum oxide as carrier, Mo and Ni is active component, and add complexing agent and additive, again after modified, obtained catalyst has very high catalytic activity, denitrification percent, desulfurization degree and Porous deproteinized bone rate after the processing of high nitrogen-containing diesel oil hydrogenation is improved, so as to improve the quality of diesel oil.
Description
Technical field
The present invention relates to the preparing technical field of catalyst, and in particular to a kind of hydrogenation suitable for high nitrogen-containing diesel oil is urged
The preparation method of agent.
Background technology
Nitrogenate in diesel oil can influence the quality, color and stability of oil product, corrode in processing and storage process
Equipment, and can discharge nitrogen oxides when as fuel oil combustion and can pollute problem to environment, so removing nitrogen therein
Compound is very important.Current oil denitrification method mainly has hydrodenitrogeneration method and Non-hydrogenation technology method, oil hydrogenation
The method of refined denitrogenation is industrially relatively conventional, is mainly used to remove sulphur, nitrogen, oxygen compound and unsaturated hydrocarbonylation in oil product
Compound, can effectively improve oil quality.In hydrogenation reaction, the effect of catalyst is particularly significant, denitrogenation, desulfurization to reaction
It is very notable with Porous deproteinized bone influential effect.In consideration of it, being necessary to study a kind of hydrogenation catalyst suitable for high nitrogen-containing diesel oil
Preparation method.
The content of the invention
To solve the deficiencies in the prior art, there is very high urge it is an object of the invention to provide a kind of obtained catalyst
Change activity, improve the hydrogenation catalyst suitable for high nitrogen-containing diesel oil of the denitrification percent after the processing of high nitrogen-containing diesel oil hydrogenation
Preparation method.
In order to realize above-mentioned target, the present invention is adopted the following technical scheme that：
Suitable for the preparation method of the hydrogenation catalyst of high nitrogen-containing diesel oil, including following preparation process：
S1, prepare aluminium hydroxide：Appropriate sodium metasilicate is weighed, is divided into 3 parts by its quality, aluminum sulfate is put in reactor, slowly
First part of sodium metasilicate is added, reactor heating function is opened, is stirred continuously down and is heated to molten condition, be slowly added to second part of silicon
Sour sodium and auxiliary agent, keep temperature of reaction kettle, persistently stir 25 ~ 45min, are slowly added to the 3rd part of sodium metasilicate, keep reaction kettle temperature
Degree, persistently stirs 30 ~ 50min, stands cooling；After cooling, temperature of reaction kettle is adjusted to 50 ~ 70 DEG C, it is lower slow being stirred continuously
Lubricating oil is added, addition speed is 2 ~ 6g/min, and addition finishes 100 ~ 120 DEG C of temperature of reaction kettle of regulation, 7 ~ 8MPa and carries out reaction 7
~ 8h, reacted product is washed three times, is dried, is crushed, obtains aluminium hydroxide powder；
S2, prepare carrier：The aluminium hydroxide powder being made and a certain amount of glacial acetic acid and deionized water are mediated, extrusion into
Type, is put in baking oven, temperature is adjusted to after 130 ~ 135 DEG C, drying 3h, taking-up is put in Muffle furnace is calcined 8 at 570 ~ 600 DEG C
After ~ 10h, alumina support is obtained；
S3, prepare metallic solution：Deionized water is added into reactor, 50 ~ 60 DEG C are adjusted the temperature to, phosphoric acid, third is slowly added to
Ketone and molybdenum trioxide, are stirred continuously 15 ~ 25min, adjust the temperature to 65 ~ 75 DEG C, are slowly added to basic nickel carbonate and ethyl acetate,
2 ~ 4 h of backflow are carried out at a temperature of 130 ~ 150 DEG C, MoNiP metallic solutions are obtained；
S4, prepare complexing agent：Citric acid, ethanedioic acid and deionized water are put in reactor, 35 ~ 42 DEG C is adjusted the temperature to, holds
15 ~ 20min of continuous stirring, is slowly added to tartaric acid, the addition speed of tartaric acid is 5 ~ 10g/min, and addition finishes, temperature is risen to
45 ~ 50 DEG C, 2.5 ~ 3.5h is persistently stirred, cooling is stood, obtains complexing agent；
S5, prepare additive：Polyethylene glycol 200 and polyethylene glycol 400 are put in reactor, 50 ~ 60 DEG C are adjusted the temperature to, delayed
It is slow to add citric acid, 20 ~ 25min is stirred, cooling is stood, obtains additive；
S6, prepare catalyst：MoNiP solution is put in reactor, complexing agent and additive is separately added into, stirring 10 ~
15min, is made mixed liquor；Alumina support is put in mixed liquor and impregnated, 7 ~ 9h of dipping is taken out, and baking oven is put in after drying
In, temperature is adjusted to 90 ~ 110 DEG C, carries out after 12 ~ 15 h of drying, places into Muffle furnace, 6 ~ 8 are calcined at 450 ~ 550 DEG C
H, takes out cooling, obtains catalyst；
S7, modification：In the mixed solution that catalyst is put in citric acid, laurate and acetone, 8 ~ 10h is impregnated, is put in after taking-up
In baking oven, temperature is adjusted to 90 ~ 110 DEG C, carries out after 6 ~ 9h of drying, obtains modified catalyst.
Preferably, in abovementioned steps S1, sodium metasilicate, aluminum sulfate, the mass ratio of auxiliary agent and lubricating oil are（25~38）：（15~
28）：（5~9）：（19~27）.
More preferably, in abovementioned steps S1, auxiliary agent is made up of following components by mass parts：15 ~ 25 parts of laurate, stearic acid
5 ~ 8 parts of 18 ~ 26 parts, 8 ~ 15 parts of ethanol, 7 ~ 10 parts of acetone, 2 ~ 7 parts of palmitic acid cetyl and urea.
It is highly preferred that in abovementioned steps S2, the mass ratio of aluminium hydroxide powder, glacial acetic acid and deionized water is（22~34）：
（15~25）：（12~20）.
It is further preferred that in abovementioned steps S3, deionized water, phosphoric acid, acetone, molybdenum trioxide, basic nickel carbonate and second
The mass ratio of acetoacetic ester is（15~23）：（18~26）：（9~16）：（30~36）：（16~23）：（3~7）.
Specifically, in abovementioned steps S4, citric acid, ethanedioic acid, the mass ratio of deionized water and tartaric acid（25~35）：（15
~20）：（8~12）：（23~34）.
Preferably, in abovementioned steps S5, the mass ratio of polyethylene glycol 200, polyethylene glycol 400 and citric acid（15~22）：
（18~26）：（17~29）.
More preferably, in abovementioned steps S6, MoNiP solution, complexing agent, the mass ratio of additive and alumina support are
（33~45）：（10~15）：（5~9）：（20~25）.
It is highly preferred that in abovementioned steps S7, catalyst, citric acid, the mass ratio of laurate and acetone are（20~25）：（13
~20）：（5~12）：（15~30）.
The present invention is advantageous in that：
（1）The preparation method of the hydrogenation catalyst suitable for high nitrogen-containing diesel oil of the present invention is simple, and the catalyst of preparation is with oxygen
Change aluminium is carrier, and Mo and Ni are active component, and adds complexing agent and additive, and there is obtained catalyst very high catalysis to live
Property, then after modified, denitrification percent, desulfurization degree and the Porous deproteinized bone rate after the processing of high nitrogen-containing diesel oil hydrogenation are improved, so as to improve
The quality of diesel oil；
（2）The addition of additive can be active metal Mo, Ni being dispersed on the surfaces externally and internally of carrier evenly, improve work
The utilization rate of property metal, so as to improve the activity of catalyst；
（3）Catalyst improves its catalytic activity, and its catalytic process is more stablized by modified.
Embodiment
Make specific introduce to the present invention below in conjunction with specific embodiment.
Embodiment 1
Suitable for the preparation method of the hydrogenation catalyst of high nitrogen-containing diesel oil, including following preparation process：
S1, prepare aluminium hydroxide：Appropriate sodium metasilicate is weighed, is divided into 3 parts by its quality, aluminum sulfate is put in reactor, slowly
First part of sodium metasilicate is added, reactor heating function is opened, is stirred continuously down and is heated to molten condition, be slowly added to second part of silicon
Sour sodium and auxiliary agent, keep temperature of reaction kettle, persistently stir 25min, are slowly added to the 3rd part of sodium metasilicate, keep temperature of reaction kettle,
30min is persistently stirred, cooling is stood；After cooling, temperature of reaction kettle is adjusted to 50 DEG C, lubrication is slowly added in the case where being stirred continuously
Oil, addition speed is 2g/min, and addition finishes 100 DEG C of temperature of reaction kettle of regulation, 7MPa and carries out reaction 7h, by reacted product
Washing three times, dries, crushes, obtain aluminium hydroxide powder；Wherein, auxiliary agent is made up of following components by mass parts：15 parts of laurate,
5 parts of 18 parts of stearic acid, 8 parts of ethanol, 7 parts of acetone, 2 parts of palmitic acid cetyl and urea；Sodium metasilicate, aluminum sulfate, auxiliary agent and lubrication
The mass ratio of oil is 25：15：5：19；
S2, prepare carrier：The aluminium hydroxide powder being made and a certain amount of glacial acetic acid and deionized water are mediated, extrusion into
Type, is put in baking oven, and temperature is adjusted to after 130 DEG C, drying 3h, and taking-up is put in Muffle furnace to be calcined after 8h at 570 DEG C, obtains oxygen
Change alumina supporter；Wherein, the mass ratio of aluminium hydroxide powder, glacial acetic acid and deionized water is 22：15：12；
S3, prepare metallic solution：Deionized water is added into reactor, 50 DEG C are adjusted the temperature to, be slowly added to phosphoric acid, acetone and
Molybdenum trioxide, is stirred continuously 15min, adjusts the temperature to 65 DEG C, is slowly added to basic nickel carbonate and ethyl acetate, in 130 DEG C of temperature
Degree is lower to carry out backflow 2h, obtains MoNiP metallic solutions；Wherein, deionized water, phosphoric acid, acetone, molybdenum trioxide, basic nickel carbonate
Mass ratio with ethyl acetate is 15：18：9：30：16：3；
S4, prepare complexing agent：Citric acid, ethanedioic acid and deionized water are put in reactor, 35 DEG C is adjusted the temperature to, persistently stirs
15min is mixed, tartaric acid is slowly added to, the addition speed of tartaric acid is 5g/min, and addition is finished, and temperature is risen into 45 DEG C, is continued
2.5h is stirred, cooling is stood, obtains complexing agent；Wherein, the mass ratio 25 of citric acid, ethanedioic acid, deionized water and tartaric acid：
15：8：23；
S5, prepare additive：Polyethylene glycol 200 and polyethylene glycol 400 are put in reactor, 50 DEG C are adjusted the temperature to, slowly
Citric acid is added, 20min is stirred, cooling is stood, obtains additive；Wherein, polyethylene glycol 200, polyethylene glycol 400 and citric acid
Mass ratio 15：18：17；
S6, prepare catalyst：MoNiP solution is put in reactor, complexing agent and additive is separately added into, 10min, system is stirred
Obtain mixed liquor；Alumina support is put in mixed liquor and impregnated, dipping 7h takes out, and is put in after drying in baking oven, by temperature
90 DEG C are adjusted to, carries out after drying 12h, places into Muffle furnace, 6 h are calcined at 450 DEG C, cooling is taken out, obtains catalyst；
Wherein, the mass ratio of MoNiP solution, complexing agent, additive and alumina support is 33：10：5：20；
S7, modification：In the mixed solution that catalyst is put in citric acid, laurate and acetone, 8 ~ 10h is impregnated, is put in after taking-up
In baking oven, temperature is adjusted to 90 DEG C, carries out after drying 6h, obtains modified catalyst；Wherein, catalyst, citric acid, laurate
Mass ratio with acetone is 20：13：5：15.
Embodiment 2
The present embodiment is identical with the preparation process in embodiment 1, and difference is the difference of concrete technology condition, including following preparation
Step：
S1, prepare aluminium hydroxide：Appropriate sodium metasilicate is weighed, is divided into 3 parts by its quality, aluminum sulfate is put in reactor, slowly
First part of sodium metasilicate is added, reactor heating function is opened, is stirred continuously down and is heated to molten condition, be slowly added to second part of silicon
Sour sodium and auxiliary agent, keep temperature of reaction kettle, persistently stir 45min, are slowly added to the 3rd part of sodium metasilicate, keep temperature of reaction kettle,
50min is persistently stirred, cooling is stood；After cooling, temperature of reaction kettle is adjusted to 70 DEG C, lubrication is slowly added in the case where being stirred continuously
Oil, addition speed is 6g/min, and addition finishes 120 DEG C of temperature of reaction kettle of regulation, 8MPa and carries out reaction 8h, by reacted product
Washing three times, dries, crushes, obtain aluminium hydroxide powder；Wherein, auxiliary agent is made up of following components by mass parts：25 parts of laurate,
8 parts of 26 parts of stearic acid, 15 parts of ethanol, 10 parts of acetone, 7 parts of palmitic acid cetyl and urea；Sodium metasilicate, aluminum sulfate, auxiliary agent and profit
The mass ratio of lubricating oil is 38：28：9：27；
S2, prepare carrier：The aluminium hydroxide powder being made and a certain amount of glacial acetic acid and deionized water are mediated, extrusion into
Type, is put in baking oven, and temperature is adjusted to after 135 DEG C, drying 3h, and taking-up is put in Muffle furnace to be calcined after 10h at 600 DEG C, is obtained
Alumina support；Wherein, the mass ratio of aluminium hydroxide powder, glacial acetic acid and deionized water is 34：25：20；
S3, prepare metallic solution：Deionized water is added into reactor, 60 DEG C are adjusted the temperature to, be slowly added to phosphoric acid, acetone and
Molybdenum trioxide, is stirred continuously 25min, adjusts the temperature to 75 DEG C, is slowly added to basic nickel carbonate and ethyl acetate, in 150 DEG C of temperature
Degree is lower to carry out 4 h of backflow, obtains MoNiP metallic solutions；Wherein, deionized water, phosphoric acid, acetone, molybdenum trioxide, basic nickel carbonate
Mass ratio with ethyl acetate is 23： 26：16：36：23：7；
S4, prepare complexing agent：Citric acid, ethanedioic acid and deionized water are put in reactor, 42 DEG C is adjusted the temperature to, persistently stirs
20min is mixed, tartaric acid is slowly added to, the addition speed of tartaric acid is 10g/min, and addition is finished, and temperature is risen into 50 DEG C, is continued
3.5h is stirred, cooling is stood, obtains complexing agent；Wherein, the mass ratio 35 of citric acid, ethanedioic acid, deionized water and tartaric acid：
20：12：34；
S5, prepare additive：Polyethylene glycol 200 and polyethylene glycol 400 are put in reactor, 60 DEG C are adjusted the temperature to, slowly
Citric acid is added, 25min is stirred, cooling is stood, obtains additive；Wherein, polyethylene glycol 200, polyethylene glycol 400 and citric acid
Mass ratio 22：26：29；
S6, prepare catalyst：MoNiP solution is put in reactor, complexing agent and additive is separately added into, 15min, system is stirred
Obtain mixed liquor；Alumina support is put in mixed liquor and impregnated, dipping 9h takes out, and is put in after drying in baking oven, by temperature
110 DEG C are adjusted to, carries out after 15 h of drying, places into Muffle furnace, 8 h are calcined at 550 DEG C, take out cooling, be catalyzed
Agent；Wherein, the mass ratio of MoNiP solution, complexing agent, additive and alumina support is 45：15：9：25；
S7, modification：In the mixed solution that catalyst is put in citric acid, laurate and acetone, 10h is impregnated, baking is put in after taking-up
In case, temperature is adjusted to 110 DEG C, carries out after drying 9h, obtains modified catalyst；Wherein, catalyst, citric acid, laurate and
The mass ratio of acetone is 25：20：12：30.
Embodiment 3
The present embodiment is identical with the preparation process in embodiment 1, and difference is the difference of concrete technology condition, including following preparation
Step：
S1, prepare aluminium hydroxide：Appropriate sodium metasilicate is weighed, is divided into 3 parts by its quality, aluminum sulfate is put in reactor, slowly
First part of sodium metasilicate is added, reactor heating function is opened, is stirred continuously down and is heated to molten condition, be slowly added to second part of silicon
Sour sodium and auxiliary agent, keep temperature of reaction kettle, persistently stir 35min, are slowly added to the 3rd part of sodium metasilicate, keep temperature of reaction kettle,
40min is persistently stirred, cooling is stood；After cooling, temperature of reaction kettle is adjusted to 60 DEG C, lubrication is slowly added in the case where being stirred continuously
Oil, addition speed is 4g/min, and addition finishes 110 DEG C of temperature of reaction kettle of regulation, 7.5MPa and carries out reaction 7.5h, will be reacted
Product is washed three times, is dried, is crushed, obtains aluminium hydroxide powder；Wherein, auxiliary agent is made up of following components by mass parts：Laurate
6 parts of 20 parts, 22 parts of stearic acid, 11 parts of ethanol, 8 parts of acetone, 5 parts of palmitic acid cetyl and urea；Sodium metasilicate, aluminum sulfate, auxiliary agent
Mass ratio with lubricating oil is 31：21：7：23；
S2, prepare carrier：The aluminium hydroxide powder being made and a certain amount of glacial acetic acid and deionized water are mediated, extrusion into
Type, is put in baking oven, and temperature is adjusted to after 132 DEG C, drying 3h, and taking-up is put in Muffle furnace to be calcined after 9h at 585 DEG C, obtains oxygen
Change alumina supporter；Wherein, the mass ratio of aluminium hydroxide powder, glacial acetic acid and deionized water is 28：20：16；
S3, prepare metallic solution：Deionized water is added into reactor, 55 DEG C are adjusted the temperature to, be slowly added to phosphoric acid, acetone and
Molybdenum trioxide, is stirred continuously 20min, adjusts the temperature to 70 DEG C, is slowly added to basic nickel carbonate and ethyl acetate, in 140 DEG C of temperature
Degree is lower to carry out backflow 3h, obtains MoNiP metallic solutions；Wherein, deionized water, phosphoric acid, acetone, molybdenum trioxide, basic nickel carbonate
Mass ratio with ethyl acetate is 19：22：12：33：19：5；
S4, prepare complexing agent：Citric acid, ethanedioic acid and deionized water are put in reactor, 38 DEG C is adjusted the temperature to, persistently stirs
17min is mixed, tartaric acid is slowly added to, the addition speed of tartaric acid is 8g/min, and addition is finished, and temperature is risen into 47 DEG C, is continued
3h is stirred, cooling is stood, obtains complexing agent；Wherein, the mass ratio 30 of citric acid, ethanedioic acid, deionized water and tartaric acid：18：
10：30；
S5, prepare additive：Polyethylene glycol 200 and polyethylene glycol 400 are put in reactor, 55 DEG C are adjusted the temperature to, slowly
Citric acid is added, 22min is stirred, cooling is stood, obtains additive；Wherein, polyethylene glycol 200, polyethylene glycol 400 and citric acid
Mass ratio 19：21：23；
S6, prepare catalyst：MoNiP solution is put in reactor, complexing agent and additive is separately added into, 13min, system is stirred
Obtain mixed liquor；Alumina support is put in mixed liquor and impregnated, dipping 8h takes out, and is put in after drying in baking oven, by temperature
100 DEG C are adjusted to, carries out after drying 13h, places into Muffle furnace, 7h is calcined at 500 DEG C, cooling is taken out, obtains catalyst；
Wherein, the mass ratio of MoNiP solution, complexing agent, additive and alumina support is 39：12：7：22；
S7, modification：In the mixed solution that catalyst is put in citric acid, laurate and acetone, 8 ~ 10h is impregnated, is put in after taking-up
In baking oven, temperature is adjusted to 100 DEG C, carries out after drying 7h, obtains modified catalyst；Wherein, catalyst, citric acid, laurate
Mass ratio with acetone is 22：16：9：22.
Comparative example 1
This comparative example is roughly the same with the preparation process in embodiment 1, and difference is in step S1, when preparing aluminium hydroxide, not
Add auxiliary agent.
Comparative example 2
This comparative example is roughly the same with the preparation process in embodiment 1, and difference is in no step S4, and in step s 6, not
Add complexing agent.
Comparative example 3
This comparative example is roughly the same with the preparation process in embodiment 1, and difference is in no step S5, and in step s 6, not
Add additive.
Comparative example 4
This comparative example is roughly the same with the preparation process in embodiment 1, and difference is no step S7.
Performance test is detected
It is obtained in Example 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 respectively to urge
Agent, for high nitrogen-containing diesel oil（Nitrogen content is 13000~16000 μ g/g）Hydroprocessing processes in, after off-test, meter
Calculate denitrification percent, desulfurization degree and the Porous deproteinized bone rate of a catalyst, concrete outcome such as following table：
As seen from the above table, the catalytic activity through catalyst made from embodiment 1, embodiment 2 and embodiment 3 be higher than comparative example 1,
Comparative example 2, comparative example 3 and comparative example 4, illustrate that through catalyst made from preparation method of the invention high nitrogen-containing bavin can be improved
Denitrification percent, desulfurization degree and the Porous deproteinized bone rate of oily hydrotreating, improve the quality of diesel oil.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Necessarily refer to identical embodiment or example.Moreover, specific features, structure, material or the feature of description can be any
One or more embodiments or example in combine in an appropriate manner.
The basic principles, principal features and advantages of the present invention have been shown and described above.The technical staff of the industry should
Understand, the invention is not limited in any way for above-described embodiment, it is all to be obtained by the way of equivalent substitution or equivalent transformation
Technical scheme, all falls within protection scope of the present invention.
Claims (9)
1. the preparation method of the hydrogenation catalyst suitable for high nitrogen-containing diesel oil, it is characterised in that including following preparation process：
S1, prepare aluminium hydroxide：Appropriate sodium metasilicate is weighed, is divided into 3 parts by its quality, aluminum sulfate is put in reactor, slowly
First part of sodium metasilicate is added, reactor heating function is opened, is stirred continuously down and is heated to molten condition, be slowly added to second part of silicon
Sour sodium and auxiliary agent, keep temperature of reaction kettle, persistently stir 25 ~ 45min, are slowly added to the 3rd part of sodium metasilicate, keep reaction kettle temperature
Degree, persistently stirs 30 ~ 50min, stands cooling；After cooling, temperature of reaction kettle is adjusted to 50 ~ 70 DEG C, it is lower slow being stirred continuously
Lubricating oil is added, addition speed is 2 ~ 6g/min, and addition finishes 100 ~ 120 DEG C of temperature of reaction kettle of regulation, 7 ~ 8MPa and carries out reaction 7
~ 8h, reacted product is washed three times, is dried, is crushed, obtains aluminium hydroxide powder；
S2, prepare carrier：The aluminium hydroxide powder being made and a certain amount of glacial acetic acid and deionized water are mediated, extrusion into
Type, is put in baking oven, temperature is adjusted to after 130 ~ 135 DEG C, drying 3h, taking-up is put in Muffle furnace is calcined 8 at 570 ~ 600 DEG C
After ~ 10h, alumina support is obtained；
S3, prepare metallic solution：Deionized water is added into reactor, 50 ~ 60 DEG C are adjusted the temperature to, phosphoric acid, third is slowly added to
Ketone and molybdenum trioxide, are stirred continuously 15 ~ 25min, adjust the temperature to 65 ~ 75 DEG C, are slowly added to basic nickel carbonate and ethyl acetate,
2 ~ 4 h of backflow are carried out at a temperature of 130 ~ 150 DEG C, MoNiP metallic solutions are obtained；
S4, prepare complexing agent：Citric acid, ethanedioic acid and deionized water are put in reactor, 35 ~ 42 DEG C is adjusted the temperature to, holds
15 ~ 20min of continuous stirring, is slowly added to tartaric acid, the addition speed of tartaric acid is 5 ~ 10g/min, and addition finishes, temperature is risen to
45 ~ 50 DEG C, 2.5 ~ 3.5h is persistently stirred, cooling is stood, obtains complexing agent；
S5, prepare additive：Polyethylene glycol 200 and polyethylene glycol 400 are put in reactor, 50 ~ 60 DEG C are adjusted the temperature to, delayed
It is slow to add citric acid, 20 ~ 25min is stirred, cooling is stood, obtains additive；
S6, prepare catalyst：MoNiP solution is put in reactor, complexing agent and additive is separately added into, stirring 10 ~
15min, is made mixed liquor；Alumina support is put in mixed liquor and impregnated, 7 ~ 9h of dipping is taken out, and baking oven is put in after drying
In, temperature is adjusted to 90 ~ 110 DEG C, carries out after 12 ~ 15 h of drying, places into Muffle furnace, 6 ~ 8 are calcined at 450 ~ 550 DEG C
H, takes out cooling, obtains catalyst；
S7, modification：In the mixed solution that catalyst is put in citric acid, laurate and acetone, 8 ~ 10h is impregnated, is put in after taking-up
In baking oven, temperature is adjusted to 90 ~ 110 DEG C, carries out after 6 ~ 9h of drying, obtains modified catalyst.
2. the preparation method of the hydrogenation catalyst according to claim 1 suitable for high nitrogen-containing diesel oil, it is characterised in that
In the step S1, sodium metasilicate, aluminum sulfate, the mass ratio of auxiliary agent and lubricating oil are（25~38）：（15~28）：（5~9）：（19~
27）.
3. the preparation method of the hydrogenation catalyst according to claim 2 suitable for high nitrogen-containing diesel oil, it is characterised in that
In the step S1, auxiliary agent is made up of following components by mass parts：15 ~ 25 parts of laurate, 18 ~ 26 parts of stearic acid, ethanol 8 ~ 15
5 ~ 8 parts of part, 7 ~ 10 parts of acetone, 2 ~ 7 parts of palmitic acid cetyl and urea.
4. the preparation method of the hydrogenation catalyst according to claim 1 suitable for high nitrogen-containing diesel oil, it is characterised in that
In the step S2, the mass ratio of aluminium hydroxide powder, glacial acetic acid and deionized water is（22~34）：（15~25）：（12~20）.
5. the preparation method of the hydrogenation catalyst according to claim 1 suitable for high nitrogen-containing diesel oil, it is characterised in that
In the step S3, deionized water, phosphoric acid, acetone, molybdenum trioxide, the mass ratio of basic nickel carbonate and ethyl acetate are（15~
23）：（18~26）：（9~16）：（30~36）：（16~23）：（3~7）.
6. the preparation method of the hydrogenation catalyst according to claim 1 suitable for high nitrogen-containing diesel oil, it is characterised in that
In the step S4, citric acid, ethanedioic acid, the mass ratio of deionized water and tartaric acid（25~35）：（15~20）：（8~12）：（23
~34）.
7. the preparation method of the hydrogenation catalyst according to claim 1 suitable for high nitrogen-containing diesel oil, it is characterised in that
In the step S5, the mass ratio of polyethylene glycol 200, polyethylene glycol 400 and citric acid（15~22）：（18~26）：（17~29）.
8. the preparation method of the hydrogenation catalyst according to claim 1 suitable for high nitrogen-containing diesel oil, it is characterised in that
In the step S6, MoNiP solution, complexing agent, the mass ratio of additive and alumina support are（33~45）：（10~15）：（5~
9）：（20~25）.
9. the preparation method of the hydrogenation catalyst according to claim 1 suitable for high nitrogen-containing diesel oil, it is characterised in that
In the step S7, catalyst, citric acid, the mass ratio of laurate and acetone are（20~25）：（13~20）：（5~12）：（15~
30）.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108371952A (en) * | 2018-02-28 | 2018-08-07 | 西京学院 | A kind of method that coordination-infusion process prepares methane-CO 2 reformation nickel-base catalyst |
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