CN107970956A - A kind of sulfurized hydrogenation catalyst and its preparation method and application - Google Patents
A kind of sulfurized hydrogenation catalyst and its preparation method and application Download PDFInfo
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- CN107970956A CN107970956A CN201610921276.2A CN201610921276A CN107970956A CN 107970956 A CN107970956 A CN 107970956A CN 201610921276 A CN201610921276 A CN 201610921276A CN 107970956 A CN107970956 A CN 107970956A
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- catalyst
- preparation
- solution
- hydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 236
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 130
- 239000002184 metal Substances 0.000 claims abstract description 113
- 238000000034 method Methods 0.000 claims abstract description 56
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011737 fluorine Substances 0.000 claims abstract description 45
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005864 Sulphur Substances 0.000 claims abstract description 33
- 239000012298 atmosphere Substances 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000011343 solid material Substances 0.000 claims abstract description 15
- -1 metals salt Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims description 56
- 239000006185 dispersion Substances 0.000 claims description 35
- 150000002739 metals Chemical class 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 15
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- 238000010438 heat treatment Methods 0.000 claims description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
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- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 8
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 16
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- 238000004073 vulcanization Methods 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 235000015393 sodium molybdate Nutrition 0.000 description 12
- 239000011684 sodium molybdate Substances 0.000 description 12
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 12
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- WSMQHVVQUCUUBN-NIRMZGPJSA-N n-(4-aminophenyl)sulfonyl-n-(3,4-dimethyl-1,2-oxazol-5-yl)acetamide;4-o-[(2r,3s,4r,6s)-4-(dimethylamino)-2-[[(3r,4s,5s,6r,7r,9r,11r,12r,13s,14r)-14-ethyl-7,12,13-trihydroxy-4-[(2r,4r,5s,6s)-5-hydroxy-4-methoxy-4,6-dimethyloxan-2-yl]oxy-3,5,7,9,11,13-hexam Chemical compound C=1C=C(N)C=CC=1S(=O)(=O)N(C(=O)C)C=1ON=C(C)C=1C.O1[C@@H](C)C[C@@H](N(C)C)[C@H](OC(=O)CCC(=O)OCC)[C@H]1O[C@H]1[C@@](O)(C)C[C@@H](C)C(=O)[C@H](C)[C@@H](O)[C@](C)(O)[C@@H](CC)OC(=O)[C@H](C)[C@@H](O[C@@H]2O[C@@H](C)[C@H](O)[C@](C)(OC)C2)[C@@H]1C WSMQHVVQUCUUBN-NIRMZGPJSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000008116 organic polysulfides Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to hydrofinishing field, discloses a kind of sulfurized hydrogenation catalyst and its preparation method and application, the described method includes：(1) solution A containing vib metals salt, sulphur source and dispersant is prepared, the solution A is in acidity；(2) solution A is contacted at 60 150 DEG C in confined conditions with catalyst carrier 5 30 it is small when；(3) group VIII metal salt and Fluorine source are introduced in the solid material as obtained by impregnating normal direction step (2) contact；(4) solid material after step (3) is impregnated roasts in inertia or reducing atmosphere.Catalyst hydrogenation performance provided by the invention is good, and preparation method is easy to operate, is easy to repeat, and catalyst preparation cost is low, and prepared catalyst is not required to presulfurization, saves on-stream time, environmentally friendly.
Description
Technical field
The present invention relates to hydrofinishing field, and in particular, to a kind of sulfurized hydrogenation catalyst and a kind of vulcanization type add
The preparation method of hydrogen catalyst and the sulfurized hydrogenation catalyst as made from the preparation method and its hydrodesulfurization and/or add
Application in hydrogen denitrogenation.
Background technology
Hydrogen addition technology is the production most important means of clear gusoline, and wherein efficient hydrogenation catalyst is then the core of hydrogen addition technology
Heart technology.Using group vib metal W or Mo as main active component, using group VIII metal Ni or Co as active ingredient is helped, with γ-A12O3
Or modified γ-A12O3Loaded catalyst for carrier is current industrial widely used hydrogenation catalyst.It is prepared by tradition
The oxidized form presoma of active component is mainly introduced to carrier duct by technology using dipping means, by aging, drying, roasting
Obtain hydrogenation catalyst.Wherein, Co, Ni, Mo and W active component exist in the form of an oxide.But hydrogenation is urged in actual use
The existence form of agent active component is the oxide morphology of Co, Ni, Mo and W, and therefore, hydrogenation catalyst must pass through before use
Vulcanization activation, is referred to as presulfurization.
Although conventional fabrication techniques obtain large-scale industrial application because of the easy to operate, advantage such as cost is low, it is still deposited
In a series of problems.On the one hand, when using oxidized form active component as presoma, no matter in dipping ageing process or in drying
Roasting process, itself and Al2O3Surface often has strong interaction, is not only easy to cause active component in carrier surface point
It is scattered uneven, the generation of excessive Al-O-Mo chemical bonds is also resulted in, then causes active component vulcanization to be difficult to completely while formed
Excessive low activity I class activity phases, active metal utilization rate are low (referring to CN 103143365A).In addition, with Mo base catalyst preparations
Exemplified by, the presoma ion Mo of generally use7O24 6-Often induce Al2O3Surface dissociation produces Al3+, then react shape
Into Anderson type heteropolyanion Al (OH)6Mo6O18 3-, it is fired generation be difficult to by full cure so as to be unfavorable for catalysis live
Property improve big crystal grain MoO3And Al2(MoO4)3Species are (referring to J.A.Bergwerff et al., Journal of the
American Chemical Society 2004,126:14548；J.A.Bergwerff et al.,Catalysis Today
2008,130:117.) hydrogenation catalyst, therefore, is difficult to realize using traditional dipping technique and has high active component dispersion degree concurrently
With high sulphidity, cause catalytic activity preferable not to the utmost.On the other hand, in conventional fabrication techniques pre-vulcanization process using
" in device " sulfurization technology, i.e., first load oxidized catalyst in hydrogenation reactor, then to anti-during continuous heating
Answer and hydrogen is passed through in device and vulcanizing agent is vulcanized, although this technology is still the technology being most widely used at present, it is still
There are a series of problems：1) vulcanization time is long, and delay goes into operation；2) sulfidation easily causes corrosion of equipment, aging；3) vulcanize
Agent is inflammable, poisonous, and easily environment is polluted；4) cost is higher etc..For " in device " sulfurization technology there are the problem of,
CN1861258A、CN1861260A、CN101088619A、CN101088620A、CN1994567A、CN101279296A、
CN101491725A, US6365542 develop a series of " outside device " sulfurization technologies, and such technology mainly includes two lines：The
A kind of technology path is first by vulcanizing agent (elementary sulfur, vegetable oil, organic sulfur compound, organic polysulfide, sulfone and sulfoxide etc.)
In the gap for the hydrogenation catalyst for introducing oxidation state using the method for distillation, melting or dipping, then exist in inert gas
Under thermally treated make catalyst vulcanization；Second of technology path be in special prevulcanisation-devices, in hydrogen and hydrogen sulfide or
The presulfurization of oxidized catalyst is completed in the presence of labile organic sulfurizing agent.Vulcanize however, no matter using " in device ", also
Be " outside device " vulcanization, be required to catalyst and first pass through oxidation state presulfurization again, cause catalyst preparation process complicated, economy compared with
Difference.
To realize that Hydrobon catalyst has greater activity component dispersion degree, and ensure active component full cure, together
When avoid the problem that " in device " sulfidation exists, simplify " outside device " vulcanize route, sulfurized hydrogenation catalyst was straight in recent years
Connect syntheti c route and obtain more and more concerns and exploration.
For example, CN1569331A discloses a kind of modified cobalt molybdenum base sulfide catalyst and preparation method thereof, pass through preparation
Ammonium thiomolybdate solution, co-precipitation molybdenum, cobalt and the third transition metal constituent element, roasts under nitrogen protection, and black powder is made
Shape catalyst.
Thio molybdic acid is dissolved in organic solvent by US6451729, and the non-negative of high-ratio surface is produced in the presence of high-temperature hydrogen
Load type MoS2Catalyst, the hydrogenation cracking activity of the catalyst are high.The shortcomings that such method is that catalyst preparation is of high cost, and only
Powder catalyst can be prepared, it is impossible to be used in large-scale hydrogenation plant.
CN1557917A discloses a kind of sulfurized hydrogenation catalyst and preparation method thereof, the preparation method master of the catalyst
If to the carrier of conventional catalyst by using soluble Thiomolybdate and thiqtung state solution by vib metals Mo
Be incorporated into the presoma of W in the gap of catalyst carrier for hydrgenating, under nitrogen protection 350 DEG C roasting 4 it is small when, then with contain Ni,
The solution dipping of Co, when 350 DEG C of roastings 4 are small under nitrogen protection, so as to prepare the supported sulfide catalysis of Mo, W, Co, Ni
Agent.Although the method can the excellent hydrogenation catalyst of processability, preparation process is complicated, the especially conjunction of vulcanization type presoma
Into complex process, cause catalyst preparation cost very high, be not suitable for heavy industrialization application.
CN102039147A discloses a kind of preparation method of sulfide type catalyst, using the alkyl containing metal Mo or W
The inorganic salts and organic additive of molybdenum sulfide (tungsten) acid ammonium salt, Ni or Co are maceration extract, by impregnating the catalyst carrier needed,
Again sulfide type catalyst is directly obtained through drying.This method preparation process is relatively simple, and preparation process is not required to inert gas shielding,
Be easily formed the high II class activity phases of catalytic activity at the same time, catalyst performance is high, but due to equally employ more difficult synthesis,
The very expensive molybdenum dithiophosphate of price (tungsten) hydrochlorate is active precursor, finally so that the manufacturing cost of catalyst is very high, application
Possibility is smaller.
To sum up, the activity of the sulfurized hydrogenation catalyst provided by the prior art increases, but raising degree has
Limit, and there are syntheti c route is complex, controllability is poor and cost is higher for the preparation method of sulfurized hydrogenation catalyst
The defects of, therefore, the commercial Application of these methods is limited to a certain extent.
The content of the invention
It is relatively low for prior art sulfurized hydrogenation catalyst activity, preparation process is complex, controllability is poor and
The defects of cost is higher, the present invention provide a kind of new sulfurized hydrogenation catalyst, the preparation method of sulfurized hydrogenation catalyst
It is de- in hydrodesulfurization and/or hydrogenation with sulfurized hydrogenation catalyst obtained by this method and above-mentioned sulfurized hydrogenation catalyst
Application in nitrogen, method provided by the invention eliminate sulfidation, prepared catalyst activity component not only high degree of dispersion,
And full cure, finally it has been obviously improved catalyst hydrogenation performance.
The present invention provides a kind of sulfurized hydrogenation catalyst, which includes carrier and the fluorine being supported on carrier
Element and active metal component, the active metal component contain group VIII metallic element and vib metals element, Section VIII
Race's metallic element and vib metals element exist with sulphided form, and the acid amount of the B acid of the catalyst is 0.1-
0.8mmol pyridines/g catalyst.
The present invention provides a kind of preparation method of sulfurized hydrogenation catalyst, which comprises the following steps：
(1) solution A containing vib metals salt, sulphur source and dispersant is prepared, the solution A is in acidity；
(2) solution A is contacted at 60-150 DEG C in confined conditions with catalyst carrier 5-30 it is small when；
(3) group VIII metal salt and Fluorine source are introduced in the solid material as obtained by impregnating normal direction step (2) contact；
(4) solid material after step (3) is impregnated roasts in inertia or reducing atmosphere；
Wherein, the sulphur source is can be in 50-100 DEG C, the sulphur-containing substance of hydrolyzed under acidic conditions；The dispersant is boiling
Point is 15-90 DEG C of water-miscible organic solvent；The Fluorine source is the water soluble compound of fluorine.
The present invention provides the sulfurized hydrogenation catalyst as made from above-mentioned preparation method.
Present invention also offers application of the above-mentioned sulfurized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrogeneration.
The present inventor is had found by studying, during sulfurized hydrogenation catalyst is prepared, first by group VIB gold
Category is contacted with after sulphur source and dispersant with carrier, is then introduced group VIII metal salt and Fluorine source, can be effectively improved sulphur
The activity of change type hydrogenation catalyst.Trace it to its cause, it may be possible to because the present invention is by directly loading host agent component (group VIB gold
Belong to) sulphided state species, not only effectively avoid the strong interaction that is produced between metal and carrier caused by defect, improve
Active metal utilization rate, and avoid adjuvant component (group VIII metal) to vulcanize prior to host agent component and cause auxiliary agent to be imitated completely
Poor situation is answered, ultimately increases the number in II classes Co (Ni)-Mo (W)-S activated centres, in addition, the present invention is by host agent
A certain amount of fluorine is introduced after component load, catalyst surface is generated a certain amount of B acid sites.The present inventor pushes away
Survey, the introducing of dispersant and fluorine generates certain influence to the structure of catalyst, and dispersant and fluorine are introduced and can produced
Certain synergistic effect, not only produces certain control action to catalyst particle size, and it is de- to promote hydrogenation to a certain extent
The formation of sulphur active sites, and be conducive to strengthen the acidity of active phase margin location-SH, so that it is guaranteed that sulfurized hydrogenation catalyst
Maintain higher activity.
In the preferred case, the present invention carries catalyst in the aqueous solution containing urea using water-soluble divalent metal
Body is modified, and can not only improve the activity of catalyst, and can effectively keep the high activity of catalyst for a long time, from
And greatly improve the service life of catalyst.It is probably because by introducing water in the aqueous solution containing urea to speculate its reason
Soluble divalent metal salt, this part aqueous divalent metal salt is in addition to it can be used as active component, and another part is then to modulation
Catalyst support surface structure, makes carrier surface form " netted " structure (such as Fig. 2 beneficial to high efficiency dispersion and anchoring activity component
It is shown).And after subsequently metal hydrogenation active component is introduced, the surface of catalyst still maintains this " netted " structure
(as shown in Figure 3).This " netted " structure not only contributes to the loading of active metal component, disperses and grappling, also effectively subtracts
Strong interaction between weak active component and carrier.
Sulfurized hydrogenation catalyst provided by the invention is sulphided state in itself, eliminates sulfidation when in use, is kept away
The complicated processes of other " outside device " vulcanization process are exempted from, have had active component high degree of dispersion and high curing degree concurrently, improve catalyst
Hydrogenation.Mentioned at the same time in CN1557917A, be loaded with the catalyst of lower valency sulfide of Mo, W, Co, Ni in room temperature
Be safe, non-hypergolic and nonflammable in relatively dry air, therefore, according to urging prepared by the method for the invention
Agent, as long as by inert gas treatment, and using room temperature is closed and lucifuge packaging, it is ensured that catalyst storage, transport and
The security of filling process.The present invention introduces fluorine and Section VIII using chemical deposition load vib metals by infusion process
Race's metal, is successfully prepared sulphided state bimetallic hydrogenation catalyst.
Compared with prior art, catalyst hydrogenation performance provided by the invention is good, and preparation method is easy to operate, is easy to weight
Multiple, catalyst preparation cost is low, and prepared catalyst is not required to presulfurization, saves on-stream time, environmentally friendly.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is unmodified γ-Al in embodiment 12O3The SEM figures of carrier surface；
Fig. 2 is the SEM figures on the alumina support Z-1 surfaces that Co is modified in embodiment 1；
Fig. 3 is the SEM figures on sulfurized hydrogenation catalyst S-1 surfaces in embodiment 1.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of sulfurized hydrogenation catalyst, which includes carrier and the fluorine being supported on carrier
Element and active metal component, the active metal component contain group VIII metallic element and vib metals element, Section VIII
Race's metallic element and vib metals element exist with sulphided form, and the acid amount of the B acid of the catalyst is 0.1-
0.8mmol pyridines/g catalyst.
A preferred embodiment of the invention, the catalyst B acid acid amount for 0.15-0.4mmol pyridines/
G catalyst.It is more advantageous to promoting the formation of hydrodesulfurization activity position using the preferred embodiment, and is conducive to enhancing activity
The acidity that phase margin location is-SH, and then further increase the Hydrogenation of catalyst.
In the present invention, it is preferred to the acid amount of the B acid of the catalyst can be 0.15-0.2mmol pyridines/g catalysis
Agent, 0.2-0.25mmol pyridines/g catalyst, 0.25-0.3mmol pyridines/g catalyst, 0.3-0.35mmol pyridines/g catalyst
Arbitrary value between 0.35-0.4mmol pyridines/g catalyst.
And the B acid acid amounts for the catalyst that the prior art provides are respectively less than 0.1mmol pyridines/g catalyst, generally 0.01-
0.08mmol pyridines/g catalyst.
In the present invention, unless otherwise specified, the acid amount of the B acid is measured by Pyridine adsorption IR spectra method, is measured
Method is：Take 10mg samples to be pressed into from blade, be fixed in infrared pond, first through vacuum (350 DEG C, 1 × 10-3Pa after) purifying 2h,
It is cooled to room temperature, scanning spectrogram is as background, at room temperature after Adsorption of Pyridine, temperature programming to measuring temperature (200 DEG C), vacuum
(1×10-3Pa it is cooled to room temperature respectively after) being desorbed 0.5h, records 1600-1400cm-1Between Pyridine adsorption IR spectra, at the same time
1545cm is obtained from spectrogram-1Locate the peak area A at peak, then pass through calculating formula A × 1000/m0(m0For unit weight, mg/cm2)
To B acid acid amounts.
Catalyst provided by the invention has active component high degree of dispersion and high curing degree concurrently, it is preferable that by X-ray electronics
The dispersion degree for the catalyst that power spectrum measures is 0.1-0.25, and sulphidity is more than 95%；The further preferred catalyst
Dispersion degree be 0.18-0.25, sulphidity 97-99%.
In the present invention, unless otherwise specified, the dispersion degree of the catalyst and sulphidity are by x-ray photoelectron spectroscopy
(XPS) measure is analyzed, wherein, dispersion degree is as the surface catalyst vib metals atom given by XPS analysis result and catalysis
Al atomic ratios represent in agent carrier, for example, when vib metals are Mo (or W), dispersion degree is represented by Mo (W)/Al.Sulphur
Change degree is obtained by XPS data processings, and specific processing method can be found in document Han et al., Journal of Materails
Chemistry2012,22:25340。
A preferred embodiment of the invention, the catalyst surface have net structure, the net structure
Mesh-density be 0.5-50/square micron, the mesh-density is by least 20 electron scanning micrographs
In lattice number per distribution in micrometer square region calculate what the method for average value measured.
, according to the invention it is preferred to the mesh-density of the net structure is 5-20/square micron.
There is no particular limitation for shooting number of the present invention for electron scanning micrograph, preferably described mesh-density
It is by calculating average value to the lattice number being distributed in every micrometer square region in 30-50 electron scanning micrographs
Method measure.
In the present invention, stereoscan photograph is obtained using S250MK3 types scanning electron microscope, and operating condition is
20kV, sample current 100mA, operating distance 24mm.
The present invention is wider to the range of choice of the content of each component in catalyst, it is preferable that using the total amount of catalyst as base
Standard, the content of the fluorine element is 1-20 weight %, and the content of carrier is 30-90 weight %, in terms of oxide, group VIII gold
The content for belonging to element is 1-25 weight %, and the content of vib metals element is 5-45 weight %.
A preferred embodiment of the invention, on the basis of the total amount of catalyst, the content of the fluorine element is
2-10 weight %, more preferably 3-7 weight %；The content of carrier is 60-90 weight %, more preferably 72-80 weights
Measure %；In terms of oxide, the content of group VIII metallic element is 1-11 weight %, more preferably 2-5 weight %；The
The content of group vib metallic element is 5-35 weight %, more preferably 15-23 weight %.
Catalytic component content uses X-ray fluorescence spectra analysis method RIPP 132-90 (Petrochemical Engineering Analysis methods
(RIPP experimental methods), Yang Cuiding, Gu Kanying, Wu Wenhui are compiled, Science Press's nineteen ninety September first edition, the 371-379 pages)
Measure.
It should be noted that exist since active metal component is actual with sulphided form, and above-mentioned metal component is with oxygen
The content meter of compound, thus causes the content of metal component smaller than actual.Obviously, when the catalyst is only containing said components
When, the content of active metal, carrier and fluorine in terms of sulfide is necessarily satisfying for 100%.
In the present invention, under preferable case, the group VIII metallic element is cobalt and/or nickel element.
In the present invention, under preferable case, the vib metals element is molybdenum and/or wolfram element.
There is no particular limitation to the carrier of the catalyst by the present invention, can be porous oxide carrier, such as can be with
For γ-Al2O3、SiO2、TiO2、SBA-15、ZrO2And SiO2-γ-Al2O3In one or more.The particularly preferred carrier is
γ-Al of the diameter in 2mm to 5mm2O3The SiO of particle or diameter in 2mm to 5mm2-γ-Al2O3Particle.Above-mentioned carrier can be with business
Buy, can also be prepared using existing method.
Sulfurized hydrogenation catalyst provided by the present invention is introduced due to fluorine so that and the acid amount of B acid increases considerably, and
The formation of hydrodesulfurization activity position is promoted to a certain extent, and is conducive to strengthen the acidity of active phase margin location-SH,
So that it is guaranteed that sulfurized hydrogenation catalyst maintains higher activity.
Present invention also offers a kind of preparation method of sulfurized hydrogenation catalyst, which comprises the following steps：
(1) solution A containing vib metals salt, sulphur source and dispersant is prepared, the solution A is in acidity；
(2) solution A is contacted at 60-150 DEG C in confined conditions with catalyst carrier 5-30 it is small when；
(3) group VIII metal salt and Fluorine source are introduced in the solid material as obtained by impregnating normal direction step (2) contact；
(4) solid material after step (3) is impregnated roasts in inertia or reducing atmosphere；
Wherein, the sulphur source is can be in 50-100 DEG C, the sulphur-containing substance of hydrolyzed under acidic conditions；The dispersant is boiling
Point is 15-90 DEG C of water-miscible organic solvent；The Fluorine source is the water soluble compound of fluorine.
In the present invention, under preferable case, the group VIII metal is cobalt and/or nickel, and the vib metals are molybdenum
And/or tungsten.
In the present invention, under preferable case, the vib metals salt is selected from sodium molybdate, sodium tungstate, ammonium tungstate, metamolybdic acid
One or more in ammonium, ammonium metatungstate, ammonium phosphomolybdate and ammonium phosphotungstate；The group VIII metal salt is selected from water soluble cobalt
And/or the one or more in the nitrate of nickel, carbonate, chlorate, sulfate and acetate.
In the case of, according to the invention it is preferred to, concentration of the vib metals salt in solution A is 0.005-5mol/L, preferably
For 0.05-0.3mol/L.
In the present invention, it is preferred to elemental metal, addition and the group VIB gold of the group VIII metal salt
The molar ratio for belonging to salt is 0.2-1.5, is preferably 0.3-0.8, is relatively beneficial to play group VIII using this kind of preferred embodiment
The synergistic effect of metal and vib metals, and the use for coordinating dispersant while the formation of active phase is relatively beneficial to, more have
Beneficial to the acidity of the active phase margin location-SH of enhancing.
In the present invention, fluorine can be introduced by its forerunner's salt form, it is had no particular limits, preferably described Fluorine source choosing
One or more from ammonium fluoride, hydrogen fluoride and sodium fluoride.
In the present invention, it is preferred in terms of fluorine element, the addition of the Fluorine source and mole of vib metals element
Than for 0.1-10, being preferably 1-8.
According to the present invention, the dispersant can be the water-miscible organic solvent that various boiling points are 15-90 DEG C, be preferably selected from
One or more in methanol, ethanol, propyl alcohol and acetone, more preferably ethanol.
The present invention is wider to the range of choice of the addition of dispersant, it is preferable that the volume of dispersant contains in the solution A
Measure as 10-90%, more preferably 30-70%.
According to the present invention, the sulphur source can be it is various can in 50-100 DEG C, the sulphur-containing substance of hydrolyzed under acidic conditions,
It is preferred that the sulphur source is thio selected from the thioamides shown in following formula (1), single monothioester shown in formula (2) and two shown in formula (3)
At least one of ester,
In formula (1), R1For NH2-、CH3-、CH3CH2-、CH3NH- or (CH3)2N-, R2And R3It is each independently H or C1-
C4 alkyl；In formula (2), R4For H or C1-C4 alkyl, R5For C1-C4 alkyl；In formula (3), R6For H or C1-C4 alkyl, R7For C1-
C4 alkyl, the C1-C4 alkyl can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group or the tert-butyl group.R2And R3
Can be identical or different.The further preferred sulphur source is the thioamides shown in formula (1), and still more preferably described sulphur source is
Thiocarbamide and/or thioacetamide, most preferably described sulphur source are thioacetamide.
In the present invention, the addition of the sulphur source is to meet to make vib metals and group VIII metal full cure
Subject to condition, under preferable case, the sulphur source and the molar ratio of group vib metallic element are 1-9：1, more preferably 3-5：1.
In the present invention, acidity refers to that pH value is less than 7.According to the present invention it is possible to make solution A be in acidity by various modes,
Such as realized by adding organic acidic substances and/or inorganic acidic materials, it is preferably added to hydrochloric acid and/or nitric acid.
In the present invention, although as long as making solution A be in acid, under preferable case, it is no more than the pH value of solution A
5, more preferably 2-5.For hydrochloric acid and nitric acid, by controlling the addition of acid and the molar ratio 0.5-3 of vib metals
By pH value control within the above range.
In the present invention, it is preferred to the solvent for forming solution A is water.
The present invention is not special to the detailed process for preparing the solution containing vib metals salt, sulphur source and dispersant
Limit, in order to be more advantageous to the scattered of each component, preferably first prepare the solution containing vib metals salt and sulphur source, Ran Houjia
Enter dispersant.It is preferred that the preparation of the solution A carries out under agitation, so that vib metals salt and sulphur source and scattered
The contact of agent is more fully, uniformly.The speed of stirring can be 10-500rpm.
A preferred embodiment of the invention, before step (2), is modified the catalyst carrier,
Modified method includes：Catalyst carrier is impregnated in the mixture containing urea, water-soluble divalent metal and water, then
It is heat-treated, filtered successively, being washed, dry and roasting.
Cause carrier surface that there is net structure using this kind of preferred embodiment, beneficial to high efficiency dispersion and anchoring activity group
Point, and subsequently by after the introducing of metal hydrogenation active component, the surface of catalyst still maintains this " netted " structure, this
" netted " structure not only contributes to the loading of active metal component, disperses and grappling, also effectively reduces active component with carrying
Strong interaction between body.
According to the present invention, in the mixture, the concentration of water-soluble divalent metal is preferably 0.01mol/L-1mol/L,
More preferably 0.1mol/L-0.5mol/L.
In accordance with the present invention it is preferred that the water-soluble divalent metal is selected from nitrate, sulfate and the chlorine of divalent metal
One or more in salt dissolving.
The divalent metal can be selected from group VIII metal, the IIth A races metal, the Ith B races metal and II B-group metal
In one or more.
In the present invention, the group VIII metallic element can be in iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum element
One or more.
IIth A races metallic element can be the one or more in calcium, magnesium, strontium and barium element.
Ith B races metallic element can be copper and/or gold element.
The II B-group metal element can be zinc and/or cadmium element.
Under preferable case, the one kind or more of the divalent metal element in cobalt, nickel, iron, calcium, magnesium, copper and Zn-ef ficiency
Kind.
According to the present invention, in the mixture, the molar ratio of the urea and water-soluble divalent metal is preferably 2-10:
1。
According to the present invention, in the mixture, the molar ratio of the catalyst carrier and water-soluble divalent metal is 3-
20：1, more preferably 4-10：1.
In accordance with the present invention it is preferred that it is 60-140 DEG C that the condition of the heat treatment, which includes heat treatment temperature, more preferably
70-90 DEG C, when heat treatment time is 2-60 small, when more preferably 12-24 is small.
There is no particular limitation to condition dry described in catalyst carrier modifying process by the present invention, can be this area
Common various drying conditions, for example, it is 100-250 DEG C that the condition of the drying, which includes drying temperature, it is preferably 100-130
DEG C, when drying time is 1-12 small, when being preferably 2-6 small.
There is no particular limitation to the condition that is roasted described in catalyst carrier modifying process by the present invention, can be this area
Common various roasting conditions, for example, it can be 400-600 DEG C that the condition of roasting, which includes calcination temperature, it is preferably 450-550
DEG C, when roasting time can be 2-10 small, when being preferably 2-6 small.
As described above, details are not described herein for the selection of the catalyst carrier.
In the present invention, for the addition of catalyst carrier in step (2), there is no particular limitation, people in the art
Member can make choice according to actual conditions, and details are not described herein, it is preferable that the addition of the catalyst carrier causes made
Standby hydrogenation catalyst, on the basis of the total amount of catalyst, the content of the fluorine element is 1-20 weight %, and the content of carrier is
30-90 weight %, in terms of oxide, the content of group VIII metallic element is 1-25 weight %, and vib metals element contains
Measure as 5-45 weight %, further preferably so that prepared hydrogenation catalyst, on the basis of the total amount of catalyst, the fluorine element
Content be 2-10 weight %, the content of carrier is 60-90 weight %, in terms of oxide, the content of group VIII metallic element
For 1-11 weight %, the content of vib metals element is 5-35 weight %.
In the present invention, step (2) contact carries out preferably in autoclave.The present invention, the autoclave refers to can
Bear 109The kettle of the pressure of Pa.
In the present invention, in preferred steps (2), solution A is connect at 80-120 DEG C in confined conditions with catalyst carrier
Touch 8-20 it is small when.
Further preferred step (2) contact carries out under agitation.It can be dried by the way that autoclave is placed in rotation
Stirring is realized by the rotation of rotary oven in case.The rotating speed of rotary oven can be 30-200rpm.
The present invention is preferably by filtering, washing, drying steps (2) contact resulting material and obtain solid material.
The present invention is to the filtering, washing, there is no particular limitation for dry condition, can be commonly used in the art
Various modes, those skilled in the art can be made choice by concrete condition, and preferably described drying carries out under an inert atmosphere.
According to the present invention, it after the drying steps, can be roasted, can not also be roasted, preferably not to dry
Solid material is roasted after dry.This kind of preferred embodiment not only simplifies catalyst preparation step, but also obtained catalyst
With more excellent Hydrogenation.
The present invention in the solid material of gained after being contacted in the step (3) to step (2) to introducing group VIII metal
There is no particular limitation for the mode of salt and Fluorine source, preferably introduces group VIII metal salt and Fluorine source by infusion process.The dipping
Method can be total immersion method, or step impregnation method, you can with by the group VIII metal salt and Fluorine source co-formulation into
Group VIII metal salt and Fluorine source, can also individually be configured to by the solid material of gained after maceration extract impregnation steps (2) contact
The solid material of gained after maceration extract impregnation steps (2) contact.It is preferred that by the group VIII metal salt and Fluorine source co-formulation
The solid material of gained after being contacted into maceration extract impregnation steps (2).
According to the present invention, the inert atmosphere can be preferably nitrogen selected from the one or more in nitrogen, argon gas and helium
Gas.
According to the present invention, the reducing atmosphere can be selected from the gas containing hydrogen and/or hydrogen sulfide.
Inert gas can be contained in the reducing atmosphere, when containing inert gas in the reducing atmosphere, hydrogen and/
Or the volume content of hydrogen sulfide is not less than 5%.
Solid material after preferably step (3) is impregnated according to the present invention roasts in a reducing atmosphere, most preferably in hydrogen
Roasted in atmosphere.The preferred embodiment is more advantageous to improving the activity of catalyst.
The present invention has no particular limits the condition roasted described in step (4), and the condition of preferably described roasting includes：
When calcination temperature is 300-800 DEG C, roasting time is 2-6 small；It is further preferred that when calcination temperature is 400-600 DEG C, roasts
Between for 3-5 it is small when.
The preparation method of sulfurized hydrogenation catalyst provided by the invention can be construed to by chemical deposition exist first
Carrier surface synthesizes the trisulfide nano particle of vib metals element, then to have loaded trisulfide nano particle
Carrier is " Second support " load regulation group VIII metal element and fluorine, then thermally treated in inertia or reducing gas to be converted into
Corresponding sulfide, so as to directly prepare supported sulfide hydrogenation catalyst.That is, the method for the present invention passes through chemistry first
Sedimentation loads vib metals, under conditions of not roasting, introduces group VIII metallic element and fluorine using infusion process, obtains
Obtained a kind of supported sulfided state hydrogenation catalyst.
Chemical deposition of the present invention may be interpreted as when sulphur source (by taking thioacetamide as an example), molybdenum salt or tungsten salt are (with molybdenum
Exemplified by sour sodium), H+And carrier is (with γ-Al2O3Exemplified by) when coexisting in same solution, using thioacetamide in low temperature, acid
Property under the conditions of slowly hydrolysis produce H2The characteristic of S, by controlling solution temperature, makes it that chemical reaction generation MoS constantly occur3It is brilliant
Grain, then make MoS3Crystal grain constantly spreads, deposits to carrier channel surfaces and obtains catalyst precursor, afterwards using it as Second support
Fluorine and group VIII metal (by taking nickel as an example) are loaded, it is finally thermally treated resulting in vulcanization type catalysis in inertia or reducing gas
Agent-NiMoS2/γ-Al2O3Method.This process can represent as follows：
3CH3CSNH2+6H2O→3CH3COONH4+3H2S↑ (1)
MoO4 2-+3H2S+2H++γ-Al2O3→MoS3/γ-Al2O3↓+4H2O (2)
The method provided according to the present invention, the occasion of introduction of the addition of dispersant, fluorine and group VIII metal are to realize
One of key of the object of the invention.To find out its cause, first aspect be probably because low-boiling dispersant (such as methanol, ethanol or
Acetone) MoS can be adsorbed to by van der Waals interaction power3Grain surface, suppresses its growth, so as to control MoS3The scale of particle,
This is that can it diffuse to carrier duct and then deposit to the premise of channel surfaces；Second aspect dispersant is combined with water, can
The boiling point of reaction solution is reduced, so that it can also reach " class hydro-thermal " environment under relatively low reaction temperature, so as to promote
MoS3Diffusion, deposition into duct；The addition of third aspect fluorine is so that the acid amount of the B acid of catalyst significantly improves, certain
The formation of hydrodesulfurization activity position is promoted in degree, and is conducive to strengthen the acidity of active phase margin location-SH；Four directions
After face is possible as vib metals introducing, fluorine and group VIII metal, fluorine and group VIII gold are introduced without roasting
Category plays vib metals more preferable modification, is more advantageous to the formation of active phase.
The sulfurized hydrogenation catalyst as made from the above method has excellent hydrodesulfurization and denitrification activity, therefore this hair
It is bright to additionally provide the sulfurized hydrogenation catalyst as made from above-mentioned preparation method and its in hydrodesulfurization and/or hydrodenitrogeneration
Using.
Below by way of the specific embodiment implementation process that the present invention will be described in detail and caused beneficial effect, it is intended to help
Where reader more clearly understands the Spirit Essence of the present invention, but any restriction cannot be formed to the practical range of the present invention.
In following embodiments, Components of Catalysts content is measured using X-ray fluorescence spectra (XRF) method, wherein, X is penetrated
Line fluorescence spectrum (XRF) method uses ZSX-100e type Xray fluorescence spectrometers, using Rh targets, in electric current 50mA, voltage 50kV's
Under the conditions of measure.
The mesh-density of catalyst and carrier surface passes through to dividing in 50 stereoscan photographs in every micrometer square region
The lattice number of cloth calculates the method measure of average value, wherein, stereoscan photograph uses S250MK3 type scanning electron microscope
Obtain, operating condition 20kV, sample current 100mA, operating distance 24mm.
The acid amount of the B acid of catalyst is measured by Pyridine adsorption IR spectra method, wherein, Pyridine adsorption IR spectra side
Method uses 560 E.S.P type FTIR spectrums analyzers (Nicolet companies of the U.S.) of Magna-IR, and specific determination condition includes：Take
10mg samples are pressed into from blade, are fixed in infrared pond, first through vacuum (350 DEG C, 1 × 10-3Pa after) purifying 2h, it is cooled to room
Temperature, scanning spectrogram is as background, at room temperature after Adsorption of Pyridine, temperature programming to measuring temperature (200 DEG C), and vacuum (1 × 10- 3Pa it is cooled to room temperature respectively after) being desorbed 0.5h, records 1600-1400cm-1Between Pyridine adsorption IR spectra, while can be from spectrum
1545cm is obtained in figure-1Locate the peak area A at peak, then pass through calculating formula A × 1000/m0(m0For unit weight, mg/cm2) obtain B
Sour amount.
The dispersion degree of host agent Mo (or W) and sulphidity are analyzed (XPS) by x-ray photoelectron spectroscopy and are measured in catalyst, its
In, dispersion degree represents that sulphidity is by XPS data as the surface metal atoms ratio (Mo (W)/Al) given by XPS analysis result
Processing obtains, and specific processing method can be found in document Han et al., Journal of Materails Chemistry
2012,22:25340, wherein, x-ray photoelectron spectroscopy analyzes (XPS) in ESCA Lab 250 model x-ray photoelectron spectroscopies
Carried out on (Britain's VG Products), use radiation source as Al K α, resolution ratio 0.5eV, be inside designated as the knot of the C1s of pollution carbon
The condition for closing energy (Eb=285.0eV) obtains.
Embodiment 1
Absolute ethyl alcohol containing 20mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.3mol/L thioacetamides are prepared, is being stirred
During, 2.4mol/L hydrochloric acid 4.0mL are added dropwise, obtain 60mL solution As, pH value 5.0；
By 4.0g diameters 2-5mm γ-Al2O3Particle (surface SEM figures are shown in Fig. 1) is dipped in 20.0mL nitre containing 0.2mol/L
Sour cobalt, 1.0mol/L urea mixed aqueous solution in, in 80 DEG C heat treatment 24 it is small when, filtering, washing then in 120 DEG C of dryings
4 it is small when, the SEM figures of the alumina support Z-1, Z-1 of Co modifications are obtained when 500 DEG C of roastings 4 are small in the air draught of 100mL/min
As shown in Figure 2.Figure it is seen that the alumina carrier surface that Co is modified has substantial amounts of net structure, mesh-density is listed in
In table 2；
Solution A is transferred in the autoclave for filling alumina support Z-1 obtained above, then by autoclave place to
24h is contacted at 85 DEG C in rotary oven (rotating speed 100rpm), then suspension is filtered, is washed, in 100 DEG C in nitrogen gas
Dry 4h, obtains MoS in atmosphere3/ Z-1 composite materials；
With 4.5mL 0.78g containing nickel nitrate, the solution of ammonium fluoride 0.46g impregnates above-mentioned MoS3/ Z-1 composite materials, room temperature are dried in the air
It is dry, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-1.Its SEM is schemed as shown in figure 3, by Fig. 3
As can be seen that " netted " structure of the two is essentially identical compared with Fig. 2, after illustrating supported active metals component, catalyst is still
" netted " structure of carrier is maintained, Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in
In table 1.Catalyst mesh-density is listed in Table 2 below.
Embodiment 2
Absolute ethyl alcohol containing 30mL, the sodium tungstate of 0.05mol/L, the aqueous solution of 0.15mol/L thioacetamides are prepared, is being stirred
During mixing, 2.4mol/L hydrochloric acid 4.0mL are added dropwise, obtain 60mL solution As, pH value 4.5；
By 4.0g diameters 2-5mm γ-Al2O3Particle is dipped in the urine of 13.0mL nickel nitrates containing 0.1mol/L, 0.4mol/L
In plain mixed aqueous solution, when 70 DEG C of heat treatments 18 are small, filtering, wash and then when 130 DEG C of dryings 2 are small, 100mL/min's
The mesh-density that the alumina support Z-2, Z-2 of Ni modifications are obtained when 550 DEG C of roastings 2 are small in air draught is listed in Table 2 below；
Solution A is transferred in the autoclave for filling alumina support Z-2 obtained above, then by autoclave place to
24h is contacted at 85 DEG C in rotary oven (rotating speed 100rpm), then suspension is filtered, is washed, in 120 DEG C in nitrogen gas
Dry 6h, obtains WS in atmosphere3/ Z-2 composite materials；
With 4.0mL 0.43g containing nickel acetate, the solution of ammonium fluoride 0.50g impregnates above-mentioned WS3/ Z-2 composite materials, room temperature are dried in the air
It is dry, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-2.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.Catalyst grid
Density is listed in Table 2 below.
Embodiment 3
Absolute ethyl alcohol containing 30mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.3mol/L thioacetamides are prepared, is being stirred
During, 2.4mol/L hydrochloric acid 4.0mL are added dropwise, obtain 60mL solution As, pH value 4.5；
By 4.0g diameters 2-5mm γ-Al2O3Particle is dipped in the urine of 20.0mL magnesium nitrates containing 0.5mol/L, 1.0mol/L
In plain mixed aqueous solution, when 90 DEG C of heat treatments 12 are small, filtering, wash and then when 100 DEG C of dryings 6 are small, 100mL/min's
The mesh-density that the alumina support Z-3, Z-3 of Mg modifications are obtained when 450 DEG C of roastings 6 are small in air draught is listed in Table 2 below.
Solution A is transferred in the autoclave for filling alumina support Z-3 obtained above, then by autoclave place to
24h is contacted at 85 DEG C in rotary oven (rotating speed 100rpm), then suspension is filtered, is washed, in 120 DEG C in nitrogen gas
Dry 6h, obtains MoS in atmosphere3/ Z-3 composite materials；
With 4.0mL 0.43g containing nickel acetate, the solution of ammonium fluoride 0.60g impregnates above-mentioned MoS3/ Z-3 composite materials, room temperature are dried in the air
It is dry, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-3.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.Catalyst grid
Density is listed in Table 2 below.
Embodiment 4
Absolute ethyl alcohol containing 40mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.45mol/L thioacetamides are prepared, is being stirred
During mixing, 2.4mol/L hydrochloric acid 4.0mL are added dropwise, obtain 60mL solution As, pH value 5.0；
Solution A is transferred to the γ-Al for filling 4.0g diameters in 2-5mm2O3In the autoclave of particle, then by autoclave
Placement contact 24h at 85 DEG C into rotary oven (rotating speed 150rpm), then suspension is filtered, is washed, in 80 DEG C in
Dry 10h, obtains MoS in nitrogen atmosphere3/γ-Al2O3Composite material；
With 4.0mL 0.78g containing cobalt nitrate, the solution of ammonium fluoride 0.70g impregnates above-mentioned MoS3/γ-Al2O3Composite material, room
Temperature is dried, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-4.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.SEM figures show,
Catalyst surface does not have net structure.
Embodiment 5
Absolute ethyl alcohol containing 30mL, the sodium molybdate of 0.15mol/L, the aqueous solution of 0.45mol/L thioacetamides are prepared, is being stirred
During mixing, 2.4mol/L hydrochloric acid 9.0mL are added dropwise, obtain 60mL solution As, pH value 2.5；
Solution A is transferred to the γ-Al for filling 8.0g diameters in 2-5mm2O3In the autoclave of particle, then by autoclave
Placement contact 24h at 85 DEG C into rotary oven (rotating speed 50rpm), then suspension is filtered, is washed, in 120 DEG C in
Dry 6h, obtains MoS in nitrogen atmosphere3/γ-Al2O3Composite material；
With 7.0mL 0.86g containing cobalt acetate, the solution of ammonium fluoride 1.0g impregnates above-mentioned MoS3/γ-Al2O3Composite material, room
Temperature is dried, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-5.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.SEM figures show,
Catalyst surface does not have net structure.
Embodiment 6
Absolute ethyl alcohol containing 30mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.3mol/L thioacetamides are prepared, is being stirred
During, 2.4mol/L hydrochloric acid 3.0mL are added dropwise, obtain 60mL solution As, pH value 5.0；
Solution A is transferred to the γ-Al for filling 2.0g diameters in 2-5mm2O3In the autoclave of particle, then by autoclave
Placement contact 24h at 85 DEG C into rotary oven (rotating speed 60rpm), then suspension is filtered, is washed, in 120 DEG C in
Dry 6h, obtains MoS in nitrogen atmosphere3/γ-Al2O3Composite material；
With 2.0mL 0.22g containing nickel acetate, the solution of ammonium fluoride 0.30g impregnates above-mentioned MoS3/γ-Al2O3Composite material, room
Temperature is dried, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-6.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.SEM figures show,
Catalyst surface does not have net structure.
Embodiment 7
Absolute ethyl alcohol containing 30mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.3mol/L thiocarbamides are prepared, in whipping process
In, 2.4mol/L hydrochloric acid 5.0mL are added dropwise, obtain 60mL solution As, pH value 4.0；
Solution A is transferred to the γ-Al for filling 5.0g diameters in 2-5mm2O3In the autoclave of particle, then by autoclave
Placement contacts 24h into rotary oven (rotating speed 200rpm) at 105 DEG C, then filters suspension, washes, in 100 DEG C
Dry 4h, obtains MoS in nitrogen atmosphere3/γ-Al2O3Composite material；
With 4.0mL 0.50g containing nickel acetate, the solution of ammonium fluoride 0.60g impregnates above-mentioned MoS3/γ-Al2O3Composite material, room
Temperature is dried, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-7.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.SEM figures show,
Catalyst surface does not have net structure.
Embodiment 8
Absolute ethyl alcohol containing 30mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.3mol/L thiocarbamides are prepared, in whipping process
In, 2.4mol/L hydrochloric acid 5.0mL are added dropwise, obtain 60mL solution As, pH value 4.0；
Solution A is transferred to the γ-Al for filling 4.0g diameters in 2-5mm2O3-SiO2In the autoclave of particle, then by height
Pressure kettle is placed contacts 24h into rotary oven (rotating speed 100rpm) at 80 DEG C, then filters suspension, washes, in 120
Dry 6h, obtains MoS DEG C in nitrogen atmosphere3/γ-Al2O3-SiO2Composite material；
With 4.0mL 0.43g containing nickel acetate, the solution of ammonium fluoride 0.60g impregnates above-mentioned MoS3/γ-Al2O3-SiO2Composite wood
Material, room temperature is dried, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-8.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.SEM figures show,
Catalyst surface does not have net structure.
Embodiment 9
Absolute ethyl alcohol containing 30mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.3mol/L thioacetamides are prepared, is being stirred
During, 2.4mol/L hydrochloric acid 4.5mL are added dropwise, obtain 60mL solution As, pH value 4.0；
Solution A is transferred to the SiO for filling 4.0g diameters in 2-5mm2-γ-Al2O3Particle (SiO2/γ-Al2O3Molar ratio
For 1：5) in autoclave, then autoclave is placed into rotary oven (rotating speed 100rpm) and contacts 24h at 75 DEG C, so
Suspension is filtered afterwards, is washed, in 120 DEG C of dry 6h in nitrogen atmosphere, obtains MoS3/SiO2-γ-Al2O3Composite material；
With 4.0mL 0.43g containing nickel acetate, the solution of ammonium fluoride 0.60g impregnates above-mentioned MoS3/SiO2-γ-Al2O3Composite wood
Material, room temperature is dried, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-9.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.SEM figures show,
Catalyst surface does not have net structure.
Embodiment 10
Method according to embodiment 1 prepares sulfurized hydrogenation catalyst, unlike, not to γ-Al2O3Particle is changed
Property, it is specially：
Absolute ethyl alcohol containing 20mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.3mol/L thioacetamides are prepared, is being stirred
During, 2.4mol/L hydrochloric acid 4.0mL are added dropwise, obtain 60mL solution As, pH value 5.0；
Solution A is transferred to the γ-Al for filling 4.0g diameters in 2-5mm2O3In the autoclave of particle, then by autoclave
Placement contact 24h at 85 DEG C into rotary oven (rotating speed 100rpm), then suspension is filtered, is washed, in 100 DEG C in
Dry 4h, obtains MoS in nitrogen atmosphere3/γ-Al2O3Composite material；
With 4.5mL 0.78g containing nickel nitrate, the solution of ammonium fluoride 0.46g impregnates above-mentioned MoS3/γ-Al2O3Composite material, room
Temperature is dried, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-10.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.SEM figures show,
Catalyst surface does not have net structure.
Embodiment 11
Method according to embodiment 1 prepares sulfurized hydrogenation catalyst, unlike, obtain MoS3/ Z-1 composite materials
Afterwards, roasting process is increased, specifically：
Absolute ethyl alcohol containing 20mL, the sodium molybdate of 0.1mol/L, the aqueous solution of 0.3mol/L thioacetamides are prepared, is being stirred
During, 2.4mol/L hydrochloric acid 4.0mL are added dropwise, obtain 60mL solution As, pH value 5.0；
By 4.0g diameters 2-5mm γ-Al2O3Particle (surface SEM figures are shown in Fig. 1) is dipped in 20.0mL nitre containing 0.2mol/L
Sour cobalt, 1.0mol/L urea mixed aqueous solution in, in 80 DEG C heat treatment 24 it is small when, filtering, washing then in 120 DEG C of dryings
4 it is small when, obtain the alumina support Z-1 of Co modifications when 500 DEG C of roastings 4 are small in the air draught of 100mL/min；
Solution A is transferred in the autoclave for filling alumina support Z-1 obtained above, then by autoclave place to
24h is contacted at 85 DEG C in rotary oven (rotating speed 100rpm), then suspension is filtered, is washed, in 100 DEG C in nitrogen gas
Dry 4h, obtains MoS in atmosphere3/ Z-1 composite materials；
By MoS3/ Z-1 composite materials are in 500 DEG C in H24h is roasted in atmosphere, obtains monometallic sulfide type catalyst MoS2/
Z-1,
With 4.5mL 0.78g containing nickel nitrate, the solution of ammonium fluoride 0.46g impregnates above-mentioned monometallic sulfide type catalyst MoS2/
γ-Al2O3, room temperature is dried, then in 500 DEG C in H24h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst S-11.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.Catalyst grid
Density is listed in Table 2 below.
Comparative example 1
NiMo/ γ-Al are prepared using room temperature equi-volume impregnating2O3Catalyst.Specially：Weigh Ammonium Molybdate Tetrahydrate
1.25g, is made into maceration extract about 10mL, and a small amount of hydrochloric acid is added dropwise to pH value about 4.5, this solution is added dropwise in vacuum state
γ-Al of the diameter of 10g in 2-5mm2O3In carrier, then place at room temperature until its natural drying, then place baking oven in
120 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain Mo/Al2O3；Nickel nitrate 0.67g and ammonium fluoride 0.50g are weighed, is made into maceration extract
8mL, impregnates 12h, 120 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain NiMo/ γ-Al at room temperature2O3, then take 1g NiMo/ γ-
Al2O3Put into miniature hydrogenation reactor " in device " vulcanize, conditions of vulcanization is：4.0MPa, 300 DEG C, 4h, hydrogen to oil volume ratio
300, sulfurized oil oil inlet flow is 8mL/h, and catalyst D-1 is obtained after vulcanization.Components of Catalysts content, dispersion degree, sulphur
The acid amount analysis result of change degree and B acid is listed in Table 1 below.SEM figures show that catalyst surface does not have net structure.
Comparative example 2
CoMo/ γ-Al are prepared using room temperature equi-volume impregnating2O3Catalyst.Specially：Weigh Ammonium Molybdate Tetrahydrate
1.25g, is made into maceration extract about 10mL, and a small amount of hydrochloric acid is added dropwise to pH value about 4.5, this solution is added dropwise in vacuum state
γ-Al of the diameter of 10g in 2-5mm2O3In carrier, then place at room temperature until its natural drying, then place baking oven in
120 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain Mo/Al2O3；Cobalt nitrate 0.67g and ammonium fluoride 0.50g are weighed, is made into maceration extract
8mL, impregnates 12h, 120 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain CoMo/ γ-Al at room temperature2O3, then as described in comparative example 1
Vulcanization process is to CoMo/ γ-Al2O3Vulcanized, obtain catalyst D-2, Components of Catalysts content, dispersion degree, sulphidity and
The acid amount analysis result of B acid is listed in Table 1 below.SEM figures show that catalyst surface does not have net structure.
Comparative example 3
NiW/ γ-Al are prepared using room temperature equi-volume impregnating2O3Catalyst.Specially：Sodium tungstate 4.80g is weighed, is made into
This solution, is added dropwise to γ-Al of the diameter in 2-5mm of the 10g in vacuum state by maceration extract about 10mL2O3In carrier, then
Place at room temperature until its natural drying, is then placed in 120 DEG C of dry 10h in baking oven, 500 DEG C of roasting 4h, obtain W/Al2O3；
Nickel nitrate 0.67g and ammonium fluoride 0.50g are weighed, is made into maceration extract 8mL, impregnates 12h, 120 DEG C of dry 10h, 500 DEG C of roastings at room temperature
4h is burnt, obtains NiW/ γ-Al2O3, then the vulcanization process as described in comparative example 1 carry out to NiW/ γ-Al2O3Vulcanized, obtained
Catalyst D-3, Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.SEM figures are aobvious
Show, catalyst surface does not have net structure.
Comparative example 4
Method according to embodiment 1 prepares sulfurized hydrogenation catalyst, unlike, it is added without when preparing solution A anhydrous
Ethanol, obtains sulfurized hydrogenation catalyst D-4, and the acid amount analysis of Components of Catalysts content, dispersion degree, sulphidity and B acid is tied
Fruit is listed in Table 1 below.Catalyst mesh-density is listed in Table 2 below.
Comparative example 5
Method according to embodiment 1 prepares sulfurized hydrogenation catalyst, unlike, hydrochloric acid is added without when preparing solution A,
The pH value of obtained solution is 7.0, obtains sulfurized hydrogenation catalyst D-5, Components of Catalysts content, dispersion degree, sulphidity
It is listed in Table 1 below with the acid amount analysis result of B acid.Catalyst mesh-density is listed in Table 2 below.
Comparative example 6
Method according to embodiment 1 prepares sulfurized hydrogenation catalyst, unlike, impregnate MoS3/γ-Al2O3Composite wood
Ammonium fluoride is added without during material, obtains sulfurized hydrogenation catalyst D-6, Components of Catalysts content, dispersion degree, sulphidity and B acid
Acid amount analysis result be listed in Table 1 below.Catalyst mesh-density is listed in Table 2 below.
Comparative example 7
Method according to embodiment 1 prepares sulfurized hydrogenation catalyst, unlike, 0.46g ammonium fluorides are first introduced molten
Liquid A, specifically, prepares absolute ethyl alcohol containing 20mL, 0.46g ammonium fluorides, the sodium molybdate of 0.1mol/L, 0.3mol/L thioacetamides
Aqueous solution, in whipping process, be added dropwise 2.4mol/L hydrochloric acid 4.0mL, obtain 60mL solution As；
Solution A is transferred in the autoclave for filling alumina support Z-1, then places autoclave to rotary oven
24h is contacted at 85 DEG C in (rotating speed 100rpm), then suspension is filtered, is washed, in 100 DEG C of dryings in nitrogen atmosphere
4h, obtains composite material；
Above-mentioned composite material is impregnated with the solution of 4.5mL 0.78g containing nickel nitrate, room temperature is dried, then in 500 DEG C in H2Gas
4h is roasted in atmosphere, obtains sulfurized hydrogenation catalyst D-7.
Components of Catalysts content, dispersion degree, sulphidity and B sour acid amount analysis result is listed in Table 1 below.Catalyst grid
Density is listed in Table 2 below.
1 Components of Catalysts content of table, dispersion degree, sulphidity and the sour of B acid measure analysis result
The mesh-density of 2 catalyst of table and carrier
| Sample number into spectrum | Mesh-density (a/square micron) |
| γ-Al2O3 | 0 |
| Z-1 | 8.9 |
| Z-2 | 6.9 |
| Z-3 | 9.6 |
| S-1 | 8.5 |
| S-2 | 10.6 |
| S-3 | 13.5 |
| S-11 | 8.9 |
| D-4 | 7.4 |
| D-5 | 9.1 |
| D-6 | 9.8 |
| D-7 | 9.0 |
The mesh-density of carrier and catalyst means its carrier and catalyst in remaining unlisted embodiment and comparative example
Surface do not have net structure.
Test example
In this test example, to the de- of the hydrogenation catalyst that is provided using hydrogenation catalyst provided by the present invention and comparative example
Sulphur and denitrification activity are evaluated in accordance with the following methods, and list result.
Hydrodesulfurization：Using the cyclohexane solution of dibenzothiophenes (DBT) mass content 1% as raw material, first weighed in Tianjin
The desulphurizing activated of catalyst is evaluated on the continuous high pressure reaction assemblies of WFSP3050 of instrument company's production.It is not required to before the reaction to urging
Agent S-1 to S-11 presulfurizations handle.Reaction condition is：4.0MPa, 340 DEG C, hydrogen to oil volume ratio 300, oil inlet flow is 8mL/
h.After stable reaction 3h, sampled after reaction 4h and reaction 1000h, sample is surveyed sulphur nitrogen instrument with HS-500 types high frequency-infrared and divided
Analysis, activity is represented with the desulfurization degree of DBT, the results are shown in Table 3.
Hydrodenitrogeneration：Using the n-heptane solution of quinoline (Q) mass content 1% as raw material, in Tianjin Xian Quan instrument companies
The denitrification activity of catalyst is evaluated on the continuous high pressure reaction assemblies of WFSP3050 of production.It is not required to before the reaction to catalyst S-1
Handled to S-11 presulfurizations.Reaction condition is：4.0MPa, 340 DEG C, hydrogen to oil volume ratio 400, oil inlet flow is 8mL/h.Reaction is steady
After determining 3h, sampled after reaction 4h and reaction 1000h, sample is surveyed sulphur nitrogen instrument with HS-500 types high frequency-infrared and analyzed, activity Q
Denitrification percent represent, the results are shown in Table 3.
Reaction desulfuration (nitrogen) rate X is calculated as follows：
The hydrodesulfurization of 3 catalyst of table, denitrification activity evaluation result
Note："-" represents not to be detected.
It can be illustrated by the result of table 1, table 2 and table 3, the hydrogenation catalyst prepared than conventional method, is carried with the present invention
For the sulfurized hydrogenation catalyst of preparation, not only with the significantly higher sour amount of B acid, preferable active component dispersion degree, higher
Sulphidity, substantially increase the utilization rate of active metal, and under preferable case, catalyst surface has net structure, more
For importantly, although two class catalyst composition it is similar, but catalyst provided by the invention have considerably better hydrogenation take off
Sulphur and denitrification activity.The above results fully show, provided by the present invention to prepare with incomparable excellent of conventional impregnation method
More property.Pass through comparative example 4, comparative example 5, comparative example 6 and comparative example 7, in the present invention, dispersant, acid solution and fluorine
The introducing of element is to ensure the key factor of the catalyst preparation technology route successful implementation.In addition, by embodiment 1 and in fact
The comparing result for applying example 10 can be seen that preferred embodiment using the present invention, can effectively extend catalyst service life.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (21)
1. a kind of sulfurized hydrogenation catalyst, which includes carrier and the fluorine element and active metal that are supported on carrier
Component, the active metal component contain group VIII metallic element and vib metals element, group VIII metallic element and
Group vib metallic element exists with sulphided form, it is characterised in that the acid amount of the B acid of the catalyst is 0.1-0.8mmol
Pyridine/g catalyst.
2. sulfurized hydrogenation catalyst according to claim 1, wherein, the acid amount of the B acid of the catalyst is 0.15-
0.4mmol pyridines/g catalyst.
3. sulfurized hydrogenation catalyst according to claim 1, wherein, the catalysis measured by X-ray electron spectrum
The dispersion degree of agent is 0.1-0.25, and sulphidity is more than 95%.
4. sulfurized hydrogenation catalyst according to claim 1, wherein, which has net structure, described
The mesh-density of net structure is 0.5-50/square micron, and the mesh-density is by being shown at least 20 scanning electrons
The lattice number being distributed in micro mirror photo in every micrometer square region calculates the method measure of average value；
Preferably, the mesh-density of the net structure is 5-20/square micron；
Preferably, the mesh-density is by every micrometer square region in 30-50 electron scanning micrographs points
The lattice number of cloth calculates the method measure of average value.
5. according to the sulfurized hydrogenation catalyst described in any one in claim 1-4, wherein, using the total amount of catalyst as base
Standard, the content of the fluorine element is 1-20 weight %, and the content of carrier is 30-90 weight %, in terms of oxide, group VIII gold
The content for belonging to element is 1-25 weight %, and the content of vib metals element is 5-45 weight %；
Preferably, the content of the fluorine element is 2-10 weight %, and the content of carrier is 60-90 weight %, in terms of oxide, the
The content of group VIII metal element is 1-11 weight %, and the content of vib metals element is 5-35 weight %.
6. according to the sulfurized hydrogenation catalyst described in any one in claim 1-5, wherein, the group VIII metal member
Element is cobalt and/or nickel element, and the vib metals element is molybdenum and/or wolfram element.
7. a kind of preparation method of sulfurized hydrogenation catalyst, it is characterised in that the preparation method comprises the following steps：
(1) solution A containing vib metals salt, sulphur source and dispersant is prepared, the solution A is in acidity；
(2) solution A is contacted at 60-150 DEG C in confined conditions with catalyst carrier 5-30 it is small when；
(3) group VIII metal salt and Fluorine source are introduced in the solid material as obtained by impregnating normal direction step (2) contact；
(4) solid material after step (3) is impregnated roasts in inertia or reducing atmosphere；
Wherein, the sulphur source is can be in 50-100 DEG C, the sulphur-containing substance of hydrolyzed under acidic conditions；The dispersant is that boiling point is
15-90 DEG C of water-miscible organic solvent；The Fluorine source is the water soluble compound of fluorine.
8. preparation method according to claim 7, wherein, the volume content of dispersant is 10-90% in the solution A,
Preferably 30-70%.
9. the preparation method according to claim 7 or 8, wherein, the dispersant is selected from methanol, ethanol, propyl alcohol and acetone
In one or more.
10. preparation method according to claim 7, wherein, the pH value of solution A is 2-5, and vib metals salt is in solution A
In concentration be 0.005-5mol/L.
11. preparation method according to claim 7, wherein, in terms of element sulphur, the sulphur source and vib metals element
Molar ratio be 1-9：1.
12. the preparation method according to claim 7 or 11, wherein, the sulphur source is selected from the thio acyl shown in following formula (1)
At least one of dithioesters shown in single monothioester and formula (3) shown in amine, formula (2),
In formula (1), R1For NH2-、CH3-、CH3CH2-、CH3NH- or (CH3)2N-, R2And R3It is each independently H or C1-C4 alkane
Base；
In formula (2), R4For H or C1-C4 alkyl, R5For C1-C4 alkyl；
In formula (3), R6For H or C1-C4 alkyl, R7For C1-C4 alkyl；
Preferably, the sulphur source is the thioamides shown in formula (1), more preferably thiocarbamide and/or thioacetamide.
13. preparation method according to claim 7, wherein, before step (2), the catalyst carrier is changed
Property, modified method includes：
Catalyst carrier is impregnated in the mixture containing urea, water-soluble divalent metal and water, then carries out heat successively
Processing, filtering, washing, dry and roasting.
14. preparation method according to claim 13, wherein, the molar ratio of the urea and water-soluble divalent metal is
2-10：1；
Preferably, the catalyst carrier and the molar ratio of water-soluble divalent metal are 3-20：1, more preferably 4-10：
1。
15. the preparation method according to claim 13 or 14, wherein, in the mixture, water-soluble divalent metal
Concentration is 0.01mol/L-1mol/L, and the water-soluble divalent metal is selected from nitrate, sulfate and the chlorination of divalent metal
One or more in salt, the divalent metal are selected from group VIII metal, the IIth A races metal, the Ith B races metal and II B-group
One or more in metal, are preferably the one or more in cobalt, nickel, iron, calcium, magnesium, copper and zinc.
16. according to the preparation method described in any one in claim 13-15, wherein, the condition of the heat treatment includes heat
Treatment temperature is 60-140 DEG C, is preferably 70-90 DEG C, when heat treatment time is 2-60 small, when being preferably 12-24 small；It is described dry
It is 100-250 DEG C that dry condition, which includes drying temperature, is preferably 100-130 DEG C, is preferably 2-6 when drying time is 1-12 small
Hour；It is 400-600 DEG C that the condition of the roasting, which includes calcination temperature, is preferably 450-550 DEG C, roasting time is small for 2-10
When, when being preferably 2-6 small.
17. preparation method according to claim 7, wherein, in step (2), by solution A and catalyst carrier in closed bar
When contact 8-20 is small at 80-120 DEG C under part.
18. preparation method according to claim 7, wherein, with elemental metal, the addition of the group VIII metal salt
Amount and the molar ratio of vib metals salt are 0.2-1.5, are preferably 0.3-0.8, in terms of fluorine element, the addition of the Fluorine source
Molar ratio with vib metals element is 0.1-10, is preferably 1-8.
19. according to the preparation method described in any one in claim 7-18, wherein, the condition bag of step (4) described roasting
Include：When calcination temperature is 300-800 DEG C, roasting time is 2-6 small.
20. the sulfurized hydrogenation catalyst as made from the preparation method described in any one in claim 7-19.
21. the sulfurized hydrogenation catalyst in claim 1-6 and 20 described in any one is in hydrodesulfurization and/or hydrodenitrogeneration
In application.
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