CN106732776B - It is a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst - Google Patents
It is a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst Download PDFInfo
- Publication number
- CN106732776B CN106732776B CN201611097417.XA CN201611097417A CN106732776B CN 106732776 B CN106732776 B CN 106732776B CN 201611097417 A CN201611097417 A CN 201611097417A CN 106732776 B CN106732776 B CN 106732776B
- Authority
- CN
- China
- Prior art keywords
- cluster
- heteropoly acid
- catalyst
- molybdenum
- nickel
- 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.)
- Active
Links
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 claims abstract description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 11
- 238000002803 maceration Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 4
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 24
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000004073 vulcanization Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- -1 Sulfo-amino salt Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 101100503316 Artemisia spiciformis FDS-1 gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 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
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of Hydrobon catalyst based on heteropoly acid cluster for presoma, it is obtained by the following method: nickel sulfate is added into Ba3/2PMo12O40 solution first, phosphato-molybdic heteropolyacid cluster is added after filtering, filtrate evaporative crystallization is taken after filtering, obtains nickel-molybdenum-phosphorus heteropoly acid cluster, then be configured to maceration extract, gamma-aluminium oxide carrier dipping is added, catalyst precursor is obtained, presoma is placed in tube furnace and is vulcanized, that is, obtains the catalyst；The catalyst dispersity is good, and activity is high, and preparation temperature is low, and method is simple, 7 MPa of stagnation pressure in autoclave, DBT hydrodesulfurization activity with higher under the conditions of 300 DEG C of reaction temperature.
Description
Technical field
The present invention relates to chemical field, it is especially a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst.
Background technique
With the exacerbation year by year of world's crude oil degree of heaviness, the continuous enhancing of Public environmental attitude, clear gusoline production
Hot spot as social concerns.2009, European Union had been carried out the Europe V standard (sulfur content≤10 μ g/g) of automotive oils, and China
State IV automotive oils standard (sulfur content≤50 μ g/g) was just implemented in full in 2015.In April, 2015, National Standards Commission require
The end of the year 2016 implemented state V automotive oils standard (sulfur content≤10 μ g/g).It is continuously increased and environmentally friendly in this motor vehicle fuel demand
Under the increasingly strict dual-pressure of regulation, China's Oil Refining Industry faces huge challenge.Currently, industrial desulfurizing oil mainly uses
Add the method for hydrogen, therefore the development of high activity hydrogenation and desulphurization catalyst is particularly important.
It is current studies have shown that the activity of Hydrobon catalyst depends primarily on its composition and preparation method, especially
Active phase precursor type.There are mainly two types of the preparation methods of Hydrobon catalyst: direct vulcanization or oxidation state vulcanization.
First method is mainly pyrolysis preparation sulphided state catalyst after carrier to load metal sulfide, and the metal sulfide of use is main
Sulfo-amino salt etc. including four thio ammonium molybdate and nickel containing auxiliary agent (cobalt).This kind of catalyst activity is higher, but the gold used
Belong to sulfide to be more toxic, production process seriously pollutes environment and complex process；Another method is will to contain ammonium molybdate, nitric acid
The maceration extract of nickel, phosphoric acid etc. is carried on carrier (such as gama-alumina, mesoporous SiO2, including MCM-41, SBA-15, HMS, SBA-
16 etc.) on, roasting, then vulcanize and catalyst is prepared.This kind of Catalyst using more, such as in the FDS-1 of petroleum urge
There is also some for agent, the FH-UDS catalyst etc. of middle petrochemical industry Fushun Petrochemical Research Institute, but the catalyst of this method preparation
Drawback, for example, this kind of maceration extract by preparations such as ammonium molybdate, nickel nitrate, phosphoric acid is a kind of nickel-molybdenum-phosphorus heteropoly acid cluster body of complexity
System, in this system, the nickel-molybdenum-phosphorus heteropoly acid cluster of various small molecules interacts, and it is living to together constitute Hydrobon catalyst
The presoma of property phase, however this system component is complicated, is difficult to determine its concrete composition, is unfavorable for the work of Hydrobon catalyst
The research of structure-activity relationship, also can not provide theoretical direction for the development of high activity hydrogenation and desulphurization catalyst between property phase and activity；
In addition, the activity of this kind of catalyst is met through Mo-O-Al bridged bond and alumina catalyst support there are stronger active force, it is unfavorable for living
The dispersion of property component；Simultaneously as molybdenum is in different precursor molecules from nickel (cobalt) auxiliary agent atom, contact is not close, unfavorable
In the generation of the active phase of the II type " Ni-Mo-S " of high activity, catalyst activity is still to be improved.
Therefore, a kind of nickel-molybdenum-phosphorus heteropoly acid cluster with specific structure is designed, is directly prepared as active phase precursor
Hydrobon catalyst, the structure activity study between hydrodesulphurizatiocatalyst catalyst activity phase and activity provide model and platform,
Accelerate desulfurizing oil process, it has also become urgent technical problem to be solved in the field.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of Hydrobon catalyst based on heteropoly acid cluster for presoma, this is urged
Agent good dispersion, activity is high, and preparation temperature is low, and preparation method is simple, easy, the present invention is implemented as follows:
It is a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst, obtain by the following method:
A) according to stoichiometric ratio to H3PMo12O40Barium hydroxide is added in solution and obtains Ba3/2PMo12O40Solution, then
According to chemical equation (1) metering than nickel sulfate is added until no longer generating new precipitating into solution, it is filtered to remove in solution
Barium sulfate precipitate；Take filtrate that phosphato-molybdic heteropolyacid cluster is added thereto according to the stoichiometric ratio of chemical equation (2) and (3)
(NH4)4H2P2Mo5O21(phosphato-molybdic heteropolyacid cluster and H be added3PMo12O40Molar ratio be 0.75:1), heat the solution system extremely
60 DEG C and continue to stir 4h, then the cooled to room temperature, (NH of generation4)3PMo12O40Due to solubility very it is low will form it is heavy
Precipitation goes out, filtering；Filtrate evaporation is taken to obtain powdered nickel-molybdenum-phosphorus heteropoly acid cluster crude product, it is miscellaneous with deionized water recrystallization nickel-molybdenum-phosphorus
Polyacid cluster crude product three times, obtains nickel-molybdenum-phosphorus heteropoly acid cluster；
Reaction equation involved in step a) is as follows:
Ba1.5PMo12O40+1.5NiSO4→Ni1.5PMo12O40+1.5BaSO4↓ (1)
(NH4)4H2P2Mo5O21+2/3Ni1.5PMo12O40→(NH4)2NiH2P2Mo5O21+2/3(NH4)3PMo12O40↓ (2)
(NH4)4H2P2Mo5O21+4/3Ni1.5PMo12O40→Ni2H2P2Mo5O21+4/3(NH4)3PMo12O40↓ (3)
B) deionized water is added in the nickel-molybdenum-phosphorus heteropoly acid cluster synthesized to step a) and is configured to maceration extract, be added at room temperature
It is dry after gamma-aluminium oxide carrier impregnates 12h, that is, obtain catalyst precursor；The catalyst precursor obtained after the completion of dipping
In, the impregnation increment of nickel-molybdenum-phosphorus heteropoly acid cluster is using the load capacity of molybdenum trioxide as gamma-aluminium oxide carrier quality on gamma-aluminium oxide carrier
The 8wt%-12wt% of score is calculated；
C) the step b) catalyst precursor obtained is placed in tube furnace, 350 DEG C of vulcanization 4h, that is, obtained described based on miscellaneous
Polyacid cluster is the Hydrobon catalyst of presoma.
Further, it is of the present invention based on heteropoly acid cluster be presoma Hydrobon catalyst, the step b) addition
Dipping is carried out in gamma-aluminium oxide carrier to refer to, gamma-aluminium oxide carrier is added in maceration extract and carries out incipient impregnation.
Further, it is of the present invention based on heteropoly acid cluster be presoma Hydrobon catalyst, step b) dipping complete
In the catalyst precursor obtained afterwards, the impregnation increment of nickel-molybdenum-phosphorus heteropoly acid cluster is on gamma-aluminium oxide carrier with the load of molybdenum trioxide
Amount is that the 12wt% of gamma-aluminium oxide carrier mass fraction is calculated.
Further, it is of the present invention based on heteropoly acid cluster be presoma Hydrobon catalyst, in step c), tube furnace
Heating rate be 10 DEG C/min.
Further, it is of the present invention based on heteropoly acid cluster be presoma Hydrobon catalyst, the step b) drying
Refer to: 120 DEG C of dry 2h.
Further, it is of the present invention based on heteropoly acid cluster be presoma Hydrobon catalyst, step a) the phosphorus molybdenum
Heteropoly acid cluster is obtained by: phosphorous acid is soluble in water, be added ammonium hydroxide simultaneously be heated to boiling, add molybdenum trioxide until
Precipitating is generated, filtering takes filtrate to boil and be concentrated by evaporation, then cools to room temperature, powdered crystal is precipitated；It filters and collects powder
Last shape crystal is dried after being washed with ice water to get to phosphato-molybdic heteropolyacid cluster, (specific steps are referring to document: Chen Weilin, Wang Enbo
The Beijing Chemistry of Polyacids [M]: Science Press, page 2013,268).
The present invention is based in the preparation process for the Hydrobon catalyst that heteropoly acid cluster is presoma, synthesis routine first is soaked
With the phosphato-molybdic heteropolyacid cluster of specific structure in stain liquid, its nickel molybdenum atom ratio is then regulated and controled by ion-exchange, finally with it
Hydrobon catalyst is prepared for active phase precursor.
Compared with prior art, the present invention is based on the hydrodesulphurizatiocatalyst catalyst activity phases that nickel-molybdenum-phosphorus heteropoly acid cluster is presoma
Structured forerunner structure determination, molecular dimension be suitable for, can for hydrodesulphurizatiocatalyst catalyst activity phase and activity between structure effect pass
System's research provides model and platform；Meanwhile the catalyst dispersity is good, activity is high, and preparation temperature is low, and method is simple, easy, warp
Overtesting is verified, catalyst prepared by the present invention stagnation pressure 7MPa in autoclave, with higher under the conditions of 300 DEG C of reaction temperature
DBT hydrodesulfurization activity.
Detailed description of the invention
Fig. 1 is the nickel-molybdenum-phosphorus heteropoly acid cluster molecule space structure of synthesis.
Fig. 2 is the phosphato-molybdic heteropolyacid cluster of synthesis and the XRD diagram of nickel-molybdenum-phosphorus heteropoly acid cluster.
Fig. 3 is the phosphato-molybdic heteropolyacid cluster of synthesis and the IR figure of nickel-molybdenum-phosphorus heteropoly acid cluster.
Fig. 4 is based on the nickel-molybdenum-phosphorus catalyst of heteropoly acid cluster and the XRD diagram of reference catalyst.
Fig. 5 is the DRIFT figure of the nickel-molybdenum-phosphorus catalyst based on heteropoly acid cluster and reference catalyst.
Specific embodiment
For convenience of understanding to technical thought of the invention, below in conjunction with specific embodiment to technical solution of the present invention into one
Step illustrates that chemical reagent and equipment involved in following embodiment are bought by commercial sources and obtained.
Tube furnace involved in embodiment is open-type vacuum/atmosphere pipe of Tianjin middle ring experimental electric furnace Co., Ltd production
Formula electric furnace, model SK-G05123K；
Gama-alumina is Shandong Aluminium Industrial Corp's product, and shape is trilobes, outer diameter 1.3mm, average length 3mm, BET
Specific surface area 289m2/ g, Kong Rong 0.7cm3/ g, aperture 8nm.
The preparation of embodiment 1 is the Hydrobon catalyst of presoma based on heteropoly acid cluster
(a) 4.1g phosphorous acid is dissolved in 70mL water, the 35wt% concentrated ammonia liquor of 7mL is then added, solution is heated to boiling,
14.4g molybdenum trioxide is added in three times into solution, is filtered after molybdenum trioxide powder dissolution, takes filtrate to boil evaporation and be allowed to body
Product is concentrated into 15-20mL, and then cooled to room temperature, is collected by filtration powdered crystal, after repeatedly being washed using 10mL ice water
It spontaneously dries in air and obtains phosphato-molybdic heteropolyacid cluster (NH4)4H2P2Mo5O21(its XRD diagram is as shown in Figure 2).
Step preparation has the phosphato-molybdic heteropolyacid cluster (NH of specific structure4)4H2P2Mo5O21Be according to document (Chen Weilin,
The Beijing Wang Enbo Chemistry of Polyacids [M]: Science Press, page 2013,268) obtain.
(b) to H3PMo12O40It suitable barium hydroxide is added in solution neutralizes it just and obtain Ba3/2PMo12O40Solution,
Then ratio is measured to Ba according to chemical equation (1)3/2PMo12O40A certain amount of nickel sulfate is added in solution；By what is generated in solution
Barium sulfate precipitate is filtered to remove, and phosphato-molybdic heteropolyacid cluster is added according to the stoichiometric ratio of chemical equation (2) and (3) in filtrate
(with H3PMo12O40Mole metering ratio 0.75)；
Ba1.5PMo12O40+1.5NiSO4→Ni1.5PMo12O40+1.5BaSO4↓ (1)
(NH4)4H2P2Mo5O21+2/3Ni1.5PMo12O40→(NH4)2NiH2P2Mo5O21+2/3(NH4)3PMo12O40↓ (2)
(NH4)4H2P2Mo5O21+4/3Ni1.5PMo12O40→Ni2H2P2Mo5O21+4/3(NH4)3PMo12O40↓ (3)
The solution system is heated to 60 DEG C and continues to be cooled to room temperature after stirring 4h, (the NH of generation4)3PMo12O40Due to
Solubility is very low to will form Precipitation, filtering.Filtrate is evaporated to obtain powdered nickel-molybdenum-phosphorus heteropoly acid cluster crude product, with go from
Sub- water recrystallization three times, obtains pure nickel-molybdenum-phosphorus heteropoly acid cluster, spatial molecular structure is as shown in Figure 1.As seen from Figure 1, Ni2+Point
It is dispersed between phosphato-molybdic heteropolyacid cluster anions, constitutes its three-D space structure.
Fig. 2 is the phosphato-molybdic heteropolyacid cluster of synthesis and the XRD diagram of nickel-molybdenum-phosphorus heteropoly acid cluster, from Figure 2 it can be seen that miscellaneous relative to phosphorus molybdenum
There is biggish offset in some diffraction maximum positions of the XRD spectra of polyacid cluster, nickel-molybdenum-phosphorus heteropoly acid cluster, this is because NH4 +It is complete
Entirely by Ni2+Replace, Ni2+Interaction force between terminal oxygen atoms makes its lattice change, and leads to some diffraction maximums
Position change.
Fig. 3 is the phosphato-molybdic heteropolyacid cluster of synthesis and the IR figure of nickel-molybdenum-phosphorus heteropoly acid cluster.As seen from Figure 3, phosphato-molybdic heteropolyacid cluster
And the IR figure of nickel-molybdenum-phosphorus heteropoly acid cluster is much like, but there is also some differences for the two: compared to the INFRARED SPECTRUM of phosphato-molybdic heteropolyacid cluster
Scheme, in the IR figure of nickel-molybdenum-phosphorus heteropoly acid cluster, 1430cm-1Place belongs to the peak and 3180cm of H-N-H-1The peak that place belongs to N-H key disappears
It loses, shows NH4 +Completely by Ni2+Substitution generates nickel-molybdenum-phosphorus heteropoly acid cluster.The XRF elemental analysis result of nickel-molybdenum-phosphorus heteropoly acid cluster
It is as shown in table 1:
The XRF elemental analysis result of 1 nickel-molybdenum-phosphorus heteropoly acid cluster of table
| Element | Nickel-molybdenum-phosphorus heteropoly acid cluster |
| Ni | 11.6 |
| Mo | 47.2 |
| O | 34.6 |
| Ni/Mo(mol) | 0.4 |
It seen from table 1, is 0.4 with the nickel-molybdenum-phosphorus heteropoly acid cluster Ni/Mo atomic ratio of XRF measuring, this is miscellaneous with nickel-molybdenum-phosphorus
Atomic ratio is consistent very much in polyacid cluster molecule formula.
(c) deionized water is added in the nickel-molybdenum-phosphorus heteropoly acid cluster synthesized to step (b) and is configured to maceration extract；By gamma oxidation
Alumina supporter, which is added in maceration extract, carries out incipient impregnation, before being put into 120 DEG C of oven drying 2h after the completion of dipping up to catalyst
Drive body；The impregnation increment that nickel-molybdenum-phosphorus heteropoly acid cluster on gamma-aluminium oxide carrier when completing is impregnated in the present embodiment is three oxygen on catalyst
The load capacity for changing molybdenum is that (in specific implementation process, the load capacity of molybdenum trioxide can control in 8wt%- 12wt% on catalyst
Between 12wt%).
(d) catalyst precursor is placed in tube furnace and is vulcanized, curing temperature is 350 DEG C, 10 DEG C/min of heating rate, sulphur
Change time 4h, that is, obtains the Hydrobon catalyst based on heteropoly acid cluster for presoma.
Reference catalyst preparation method: it is prepared with ammonium molybdate, nickel nitrate, phosphoric acid (three's molar ratio is followed successively by 5:14:14)
Gamma-aluminium oxide carrier is added in maceration extract and carries out incipient impregnation by maceration extract, and it is dry that 120 DEG C of baking ovens are put into after the completion of dipping
Dry 2h obtains catalyst precursor；The catalyst precursor of acquisition is placed in tube furnace and is vulcanized, curing temperature is 400 DEG C, is risen
Warm 10 DEG C/min of rate, vulcanization time 4h, i.e. acquisition reference catalyst, the load capacity of molybdenum trioxide is 12wt%, with this reality
The nickel-molybdenum-phosphorus catalyst based on heteropoly acid cluster for applying example acquisition is identical.
Fig. 4 is the present embodiment acquisition based on the nickel-molybdenum-phosphorus catalyst of heteropoly acid cluster and the XRD diagram of reference catalyst, by scheming
4 as it can be seen that there is (NH in reference catalyst4)4H6NiMo6O24·5H2The diffraction maximum of O shows that nickel molybdenum component is agglomerated into phase, dispersion
It spends poor.And (NH is not occurred based on the catalyst that nickel-molybdenum-phosphorus heteropoly acid cluster is presoma4)4H6NiMo6O24·5H2The diffraction of O
Peak shows its nickel molybdenum component dispersibility preferably, and crystal grain of the nickel molybdenum component with unformed or size less than 4nm exists.
Fig. 5 is the DRIFT spectrogram of the nickel-molybdenum-phosphorus catalyst based on heteropoly acid cluster that the present embodiment obtains and reference catalyst.
As seen from Figure 5, two kinds of catalyst are in 2090 and 2062cm-1Nearby all there are two apparent CO absorption peak, but peak intensity difference compared with
Greatly.The absorption peak strength (Ni-Mo-S active sites) of nickel-molybdenum-phosphorus catalyst based on heteropoly acid cluster is apparently higher than reference catalyst.Table
The nickel-molybdenum-phosphorus catalyst surface based on heteropoly acid cluster that bright the present embodiment obtains contains more Ni-Mo-S active sites, and catalysis is lived
Property is higher.
To the present embodiment acquisition based on the nickel-molybdenum-phosphorus catalyst of heteropoly acid cluster and the hydrodesulfurization activity of reference catalyst
Evaluation, (detection method is referring to W.Han, P.Yuan, Y.Fan, G.Shi, H.Liu, D.Bai, X.Bao, Preparation of
supported hydrodesulfurization catalysts with enhanced performance using Mo-
based inorganic-organic hybrid nanocrystals as a superior precursor,Journal
Of Materials Chemistry, 22 (2012) 25340-25353.), the results are shown in Table 2:
Hydrodesulfurization activity and the hydrogenolysis selectivity of 2 catalyst of table
In table 2, the 1 nickel-molybdenum-phosphorus catalyst based on heteropoly acid cluster obtained for the present embodiment, 2 is using conventional forerunner's systems
The reference catalyst of the standby load capacity containing same metal.As can be seen from Table 2, the nickel based on heteropoly acid cluster that the present embodiment obtains
The DBT conversion ratio and reaction rate constant k of molybdenum phosphorus catalystDBTIt is higher than reference catalyst, show that its catalytic activity is higher.Together
When, it can be seen from distribution of reaction products the present embodiment obtain the nickel-molybdenum-phosphorus catalyst based on heteropoly acid cluster be more likely into
Row HYD reaction path.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (4)
1. it is a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst, obtain by the following method:
A) to H3PMo12O40Barium hydroxide is added in solution and obtains Ba3/2PMo12O40Solution adds nickel sulfate until no longer producing
Raw new precipitating, filtering；Phosphato-molybdic heteropolyacid cluster (NH is added into filtrate4)4H2P2Mo5O21, heated solution system to 60 DEG C simultaneously
4 h are persistently stirred, are then cooled to room temperature, are filtered;Filtrate evaporation is taken to obtain nickel-molybdenum-phosphorus heteropoly acid cluster crude product, with deionized water
Recrystallization three times to get arrive nickel-molybdenum-phosphorus heteropoly acid cluster；
Wherein, phosphato-molybdic heteropolyacid cluster (NH be added4)4H2P2Mo5O21With H3PMo12O40Molar ratio be 0.75:1；
B) deionized water is added in the nickel-molybdenum-phosphorus heteropoly acid cluster synthesized to step a) and is configured to maceration extract, gama-alumina is added and carries
It is dry after body impregnates 12 h, that is, obtain catalyst precursor；
In the catalyst precursor, the load capacity of molybdenum trioxide is 12wt% on gamma-aluminium oxide carrier；
Dipping is carried out in the addition gamma-aluminium oxide carrier to refer to, gamma-aluminium oxide carrier is added in maceration extract and is carried out in equal volume
Dipping；
C) catalyst precursor that step b) obtains is placed in tube furnace, 350 DEG C of 4 h of vulcanization, that is, obtained described based on miscellaneous more
Sour cluster is the Hydrobon catalyst of presoma.
2. being according to claim 1 the Hydrobon catalyst of presoma based on heteropoly acid cluster, which is characterized in that step c)
In, the heating rate of tube furnace is 10 DEG C/min.
3. being according to claim 2 the Hydrobon catalyst of presoma based on heteropoly acid cluster, which is characterized in that step b)
The drying refers to: 120 DEG C of 2 h of drying.
4. being according to claim 1 the Hydrobon catalyst of presoma based on heteropoly acid cluster described in one of -3, which is characterized in that
Phosphato-molybdic heteropolyacid cluster (NH described in step a)4)4H2P2Mo5O21It is obtained by: phosphorous acid is soluble in water, ammonium hydroxide is added simultaneously
It is heated to boiling, adds molybdenum trioxide until generating precipitating, filtering takes filtrate to boil and be concentrated by evaporation, is subsequently cooled to room
Powdered crystal is precipitated in temperature；It filters and collects powdered crystal, dried after being washed with ice water to get the phosphato-molybdic heteropolyacid is arrived
Cluster (NH4)4H2P2Mo5O21。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611097417.XA CN106732776B (en) | 2016-12-02 | 2016-12-02 | It is a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611097417.XA CN106732776B (en) | 2016-12-02 | 2016-12-02 | It is a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106732776A CN106732776A (en) | 2017-05-31 |
| CN106732776B true CN106732776B (en) | 2019-07-12 |
Family
ID=58883108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611097417.XA Active CN106732776B (en) | 2016-12-02 | 2016-12-02 | It is a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732776B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058281B (en) * | 2020-05-14 | 2023-02-17 | 哈尔滨理工大学 | Preparation and application of bimetallic sulfide crystal derived from cobalt germanomolybdenum polyacid complex |
| WO2022201179A1 (en) | 2021-03-20 | 2022-09-29 | Hindustan Petroleum Corporation Limited | A dispersed hydrotreating catalyst and a process of preparation thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773438A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Distillate oil hydro-desulfurization method |
| CN104549519A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
-
2016
- 2016-12-02 CN CN201611097417.XA patent/CN106732776B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773438A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Distillate oil hydro-desulfurization method |
| CN104549519A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
Non-Patent Citations (2)
| Title |
|---|
| "Hydroprocessing catalysts based on transition metal sulfides prepared from Anderson and dimeric Co2Mo10- heteropolyanions: A review";Pavel Nikulshin 等;《Comptes Rendus Chimie》;20160104;第19卷;第1276-1285页 |
| "Waugh-Type NiMo Heteropolycompounds as More Effective Precursors of Hydrodesulfurization Catalyst";Jilei Liang等;《Catal Lett》;20140806;第144卷;第1735-1744页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106732776A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Song et al. | Preparation of composite TiO2–Al2O3 supported nickel phosphide hydrotreating catalysts and catalytic activity for hydrodesulfurization of dibenzothiophene | |
| ES2768079T3 (en) | Mixed transition metal oxides and preparation procedure | |
| JP6273090B2 (en) | Solutions and catalysts containing Group 6 metals, Group 8 metals and phosphorus | |
| KR101751923B1 (en) | Hydrodesulfurization catalyst and preparing method thereof | |
| CN106179474B (en) | A kind of Hydrobon catalyst and its preparation method | |
| KR101782775B1 (en) | Concentrated solutions comprising group ⅵ metal, group ⅷ metal, and phosphorus | |
| CN105521792B (en) | A kind of load type double-metal hydrogenation catalyst and its preparation method and application | |
| CN105008041B (en) | New catalyst for hydrotreatment of residual oil | |
| CN106179381A (en) | The preparation method of Hydrobon catalyst | |
| CN106732776B (en) | It is a kind of based on heteropoly acid cluster be presoma Hydrobon catalyst | |
| US11524278B2 (en) | Hydrotreating catalyst with a titanium containing carrier and sulfur containing organic additive | |
| CN106268965A (en) | A kind of hydrocracking catalyst containing Beta molecular sieve and application thereof | |
| US11420193B2 (en) | Hydrotreating catalyst with a titanium containing carrier and organic additive | |
| CN105102123A (en) | Carrier for hydrogenation catalysts, method for producing same, hydrogenation catalyst and method for producing hydrogenation catalyst | |
| CN103627425A (en) | Residual oil hydro-desulfurization method | |
| CN106179377B (en) | A kind of preparation method of Hydrobon catalyst composition | |
| CN106693997B (en) | A kind of diesel hydrogenation for removal sulphur catalyst and its preparation method and application | |
| CN106179388A (en) | A kind of preparation method of hydrotreating catalyst | |
| CN102380412B (en) | Method for preparing MFI catalyst carrying transition elements and MFI catalyst application | |
| CN104971731A (en) | Wide-temperature sulfur-tolerance shift catalyst and preparation method therefor | |
| CN109603839B (en) | Preparation method of bulk cobalt-molybdenum hydrodesulfurization catalyst | |
| CN106669713B (en) | The preparation method of hydrotreating catalyst | |
| CN106179380B (en) | A kind of Hydrobon catalyst and preparation method thereof | |
| CN115463664B (en) | Preparation method of high-dispersion organic sulfur hydrogenation catalyst | |
| CN106179389A (en) | Hydrobon catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230825 Address after: Room 12-15, Building B, Window of the World Industrial Park, No. 451, Mount Huangshan Road, Shushan District, Hefei City, Anhui Province, 230000 Patentee after: Anhui Zhongzhi Zhonghui Enterprise Management Service Co.,Ltd. Address before: No. 100, Chunhui Road, Hailing District, Taizhou City, Jiangsu Province, 225300 Patentee before: TAIZHOU University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240509 Address after: No. 799, Weiyang fifth road, Gaoling District, Xi'an City, Shaanxi Province, 710200 Patentee after: SHAANXI AEROSPACE DELIN SCIENCE AND TECHNOLOGY GROUP CO.,LTD. Country or region after: China Patentee after: SHAANXI SPACE PUMP & VALVE SCIENCE AND TECHNOLOGY CO.,LTD. Address before: Room 12-15, Building B, Window of the World Industrial Park, No. 451, Mount Huangshan Road, Shushan District, Hefei City, Anhui Province, 230000 Patentee before: Anhui Zhongzhi Zhonghui Enterprise Management Service Co.,Ltd. Country or region before: China |