CN110508294A - Hydrogenation catalyst preparation method and by this method preparation hydrogenation catalyst and application - Google Patents
Hydrogenation catalyst preparation method and by this method preparation hydrogenation catalyst and application Download PDFInfo
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- CN110508294A CN110508294A CN201810485163.1A CN201810485163A CN110508294A CN 110508294 A CN110508294 A CN 110508294A CN 201810485163 A CN201810485163 A CN 201810485163A CN 110508294 A CN110508294 A CN 110508294A
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to hydrofinishing fields, disclose a kind of hydrogenation catalyst preparation method and catalyst and application by this method preparation, the preparation method includes the following steps: that tetrathiomolybdate and group VIII metal salt are introduced on carrier by (1), obtains composite A；(2) composite A is heat-treated under inert atmosphere or reducing atmosphere, so that Mo exists in the form of trisulfide in composite A, group VIII metallic element exists in a salt form for the heat treatment.Preparation method provided by the invention eliminates sulfidation, prepared catalyst activity component full cure, and catalyst hydrogenation performance is obviously improved.
Description
Technical field
The present invention relates to hydrofinishing fields, more particularly to a kind of hydrogenation catalyst preparation method and have this method preparation
Hydrogenation catalyst and the application in hydrodesulfurization.
Background technique
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.It is to help active constituent with group VIII metal Ni or Co, with γ-A1 with group vib metal W or Mo for main active component2O3
Or modified γ-A12O3Loaded catalyst for carrier is current industrial widely used hydrogenation catalyst.Tradition preparation
Technology mainly uses dipping means that the oxidized form presoma of active component is introduced to carrier duct, by aging, drying, roasting
Obtain hydrogenation catalyst.Wherein, Co, Ni, Mo and W active component exist in the form of an oxide.But in actual use plus hydrogen is urged
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
Vulcanization activation, referred to as presulfurization.
Although conventional fabrication techniques obtain large-scale industrial application due to the advantages that easy to operate, at low cost, still deposit
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, with Al2O3Surface often has strong interaction, is not only easy to cause active component in carrier surface point
It dissipates unevenly, also results in the generation of excessive Al-O-Mo chemical bond, then cause active component to be difficult to complete cure, while easily
Excessive low activity I class activity phase is formed, active metal utilization rate is low (referring to CN 103143365A).In addition, with Mo base catalyst
For preparation, the presoma ion Mo that generallys use7O24 6-Often induce Al2O3Surface dissociation generates Al3+, then anti-therewith
Anderson type heteropolyanion Al (OH) should be formed6Mo6O18 3-, it is fired generation and is difficult to by the big crystal grain MoO of full cure3
And Al2(MoO4)3Species improve to be unfavorable for catalytic activity (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.), therefore, hydrogenation catalyst is difficult to realize using traditional dipping technique and has both high active component
Dispersion degree and high sulphidity, cause catalytic activity ideal not to the utmost.On the other hand, pre-vulcanization process uses in conventional fabrication techniques
Be " in device " sulfurization technology, i.e., first oxidized catalyst is packed into hydrogenator, then during continuous heating
It is passed through hydrogen into reactor and vulcanizing agent is vulcanized, although this technology is still the technology being most widely used at present, it
Still remain a series of problems: 1) vulcanization time is too long, and delay goes into operation；2) sulfidation easily causes corrosion of equipment, aging；3)
Vulcanizing agent is inflammable, toxic, easily pollutes the environment；4) higher cost etc.." in device " sulfurization technology there are aiming at the problem that,
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.)
It is introduced into using the method for distillation, melting or dipping in the gap of the hydrogenation catalyst of oxidation state, is then existed 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.However, no matter being vulcanized 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 guarantee active component full cure, together
When avoid the problem that sulfidation exists " in device ", simplify " outside device " vulcanize route, sulfurized hydrogenation catalyst was straight in recent years
It connects preparation route and has obtained 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 generated in the presence of high-temperature hydrogen
Load type MoS2The hydrogenation cracking activity of catalyst, the catalyst is high.The shortcomings that such method, is that catalyst preparation is at 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 introduced into the gap of catalyst carrier for hydrgenating with the presoma of W, under nitrogen protection 350 DEG C roast 4 hours, then with contain Ni,
The solution of Co impregnates, and roasts 4 hours for 350 DEG C under nitrogen protection, to prepare the supported sulfide catalysis of Mo, W, Co, Ni
Agent.Preparing in Thiomolybdate and thiqtung state solution processes joined organic solvent, during the high temperature treatment process, due to having
The volatilization of solvent strengthens the interaction of active metal component and carrier, affects the vulcanization of active metal, so that metal
Sulphidity is lower, influences the activity and selectivity of catalyst.
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,
Sulfide type catalyst is directly obtained through drying again.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 phase of catalytic activity simultaneously, catalyst service performance is high, but due to equally use more difficult synthesis,
Price very expensive molybdenum dithiophosphate (tungsten) hydrochlorate is active precursor, finally makes the preparation cost of catalyst very high, application
Possibility is smaller.
CN104707629A discloses a kind of preparation method of carrier-borne transition metal sulfide hydrogenation catalyst, this method
High-sulfur is prepared by liquid impregnation absorption-deposition-high temperature reduction three-step approach using tetrathiomolybdate and soluble nickel, cobalt salt
Ni (Co) MoS Hydrobon catalyst of change degree.Compared with preceding method, this method avoid template, alkaline solution and have
The use of solvent.However, the preparation method, in the certain situation of liquor capacity, in liquid impregnation adsorption process, activity is golden
It is uncontrollable to belong to load capacity, it is difficult to adjust the relative atom ratio for helping active component Ni (Co) Yu main active component Mo；In addition, adsorbing
When balance is with precipitating, there are still the active metal components that can not be loaded on carrier in solution, metal utilization is low, causes original
Material loss.
To sum up, the activity of the sulfurized hydrogenation catalyst provided by the prior art increases, but raising degree has
Limit, and that there are preparation routes is complex, controllability is poor and higher cost for the preparation method of sulfurized hydrogenation catalyst
Defect therefore limit the industrial application of these methods to a certain extent.
Summary of the invention
It is lower for prior art activity of hydrocatalyst, preparation process is complex, controllability is poor and cost compared with
High defect, the present invention provide a kind of new hydrogenation catalyst preparation method and hydrogenation catalyst obtained by this method and
Application of the above-mentioned hydrogenation catalyst in hydrodesulfurization, preparation method provided by the invention eliminates sulfidation, prepared
Catalyst activity component full cure, catalyst hydrogenation performance are obviously improved.
The present invention provides a kind of preparation method of hydrogenation catalyst, include the following steps: (1) by tetrathiomolybdate and
Group VIII metal salt is introduced on carrier, obtains composite A；(2) to composite A under inert atmosphere or reducing atmosphere
It is heat-treated, the heat treatment is so that Mo exists in the form of trisulfide in composite A, and group VIII metallic element is with salt
Form exist.
The present invention provides the hydrogenation catalysts as made from above-mentioned preparation method.
The present invention also provides application of the above-mentioned hydrogenation catalyst in hydrodesulfurization.
The present inventor passes through the study found that during preparing hydrogenation catalyst, first by tetrathiomolybdate and
Group VIII metal salt is introduced on carrier, obtains composite A；Then to composite material under inert atmosphere or reducing atmosphere
A is heat-treated, the heat treatment so that Mo exists in the form of trisulfide in composite A, group VIII metallic element with
The form of salt exists, and the preferable hydrogenation catalyst of Hydrogenation can be obtained.
Hydrogenation catalyst provided by the invention only needs catalyst simple thermal treatment catalysis can be realized in start-up process
The activation of agent is not necessarily to sulfidation, therefore is conducive to substantially save on-stream time, saves the cost that goes into operation, reduces the safety of refinery
Risk.
In the preferred case, tetrathiomolybdate and group VIII metal salt are introduced on carrier described in step (1)
Method are as follows: prepare tetrathiomolybdate solution, thereto add group VIII metal salt formed mixed solution, using the mixing
Solution impregnates carrier, is then dried；Or tetrathiomolybdate solution and metal containing group VIII is respectively adopted
The solution of salt impregnates carrier, is dried after dipping every time.
It is further preferred that the tetrathiomolybdate solution is made by following methods: a) by molybdate compound, organic
Sulphur source and water mixing；B) mixture obtained by step a) is reacted into 2-24h under the conditions of being 5-10 for 50-100 DEG C and/or pH；It is described
Organic sulphur source is the sulphur-containing substance that can be hydrolyzed under the conditions of step a) and/or step b).The work of catalyst can not only be improved
Property, and do not need to crystallize out tetrathiomolybdate, directly urged by maceration extract preparation plus hydrogen of tetrathiomolybdate solution
Agent not only simplifies operating procedure, and overcomes in the prior art since Thiomolybdate price is very expensive, application
The lesser defect of possibility.
Compared with prior art, hydrogenation catalyst provided by the invention has the advantages that
(1) Mo itself is sulphided state in hydrogenation catalyst provided by the invention, it is possible to prevente effectively from metal and carrier it
Between a series of problems brought by strong interaction, can successfully avoid auxiliary agent Co (Ni) from vulcanizing before it, improve activity gold
Belong to utilization rate, obtains II class Co (Ni)-Mo-S activity phase of high activity；
(2) Mo exists in the form of trisulfides state in hydrogenation catalyst provided by the invention, only needs before going into operation to catalyst
Simple reduction treatment is carried out, adjuvant component can be vulcanized (MoS3It is converted into MoS2, group VIII metal salt is converted into Section VIII
The sulfide of race's metal), and II class Co (the Ni)-Mo-S activity phase with greater catalytic performance is obtained, catalyst need not pre- sulphur
Change, saves on-stream time, it is environmental-friendly；
(3) present invention directly impregnates carrier using tetrathiomolybdate solution, can effectively improve metal utilization
Rate.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, 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 the ultraviolet-visible absorption spectroscopy figure (UV-Vis) for the tetrathiomolybdate solution that embodiment 1 obtains；Fig. 2 is
The XRD diffracting spectrum for the hydrogenation catalyst S-1 that embodiment 1 obtains.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of hydrogenation catalyst, the preparation method the following steps are included: (1) by four sulphur
It is introduced on carrier for molybdate and group VIII metal salt, obtains composite A；(2) under inert atmosphere or reducing atmosphere
Composite A is heat-treated, the heat treatment is so that Mo exists in the form of trisulfide in composite A, group VIII
Metallic element exists in a salt form.
In the present invention, it is preferable that tetrathiomolybdate and group VIII metal salt are introduced into carrier described in step (1)
On method are as follows: prepare tetrathiomolybdate solution, add group VIII metal salt thereto and form mixed solution, it is mixed using this
It closes solution to impregnate carrier, then be dried；Or tetrathiomolybdate solution is respectively adopted and contains group VIII gold
The solution for belonging to salt impregnates carrier, is dried after dipping every time.
In order to further increase the Hydrogenation of catalyst obtained, simplify operating procedure, and reduce catalyst production
Cost, preferably tetrathiomolybdate solution are made by following methods:
A) molybdate compound, organic sulphur source and water are mixed；
B) mixture obtained by step a) is reacted into 2-24h under the conditions of being 5-10 for 50-100 DEG C and/or pH；
Organic sulphur source is the sulphur-containing substance that can be hydrolyzed under the conditions of step a) and/or step b).
According to the present invention, wider to the range of choice of the concentration of the tetrathiomolybdate solution, those skilled in the art
It can be selected according to the actual situation.For example, in order to load the molybdenum of specific quantity four sulphur can be calculated by the water absorption rate of carrier
For the concentration of molybdate solution.The concentration of tetrathiomolybdate solution appropriate in order to obtain, can be by obtained above
Tetrathiomolybdate solution is concentrated or is diluted.It is preferred that the concentration of the tetrathiomolybdate solution is 0.2-1.8mol/
L, further preferably 0.3-1.2mol/L.
By means of the present invention, tetrathiomolybdate is directly utilized, active metal component can be efficiently used, avoid living
The waste of property metal.
Only containing a small amount of volatile foreign ion in above-mentioned tetrathiomolybdate solution provided by the invention, such as
CH3COO-、NH4 +, in subsequent catalyst preparation process, in heat treatment or drying process, it can remove naturally, therefore, this hair
The method of bright offer can not need crystallization and purification and obtain by the tetrathiomolybdate solution of above-mentioned acquisition directly as maceration extract
Tetrathiomolybdate is dissolved again as maceration extract, and operating procedure is simplified.
The prior art mostly uses hydrogen sulfide as sulphur source, in order to enable molybdenum in preparing tetrathiomolybdate solution processes
Source is substantially soluble in water, adds into cosolvent, such as ammonium hydroxide, so that being needed in entire tetrathiomolybdate solution processes using having
The ammonium hydroxide of penetrating odor, and can not overcome the problems, such as the hydrogen sulfide gas for needing to handle severe toxicity, stench.And it is provided by the invention
During preparing tetrathiomolybdate solution, molybdate compound, organic sulphur source and water are mixed；Then pass through heating mixture
And/or add acid-base accommodation mixture pH so that organic sulphur source completely dissolves in water, during the reaction, molybdate compound with
O-S exchange reaction is sufficiently carried out between organic sulphur source.
The present invention is wider to the range of choice for the mode that the molybdate compound, organic sulphur source and water mix, it is preferable that step
Rapid a) the described mixing includes: that molybdate compound is dissolved in water to form the first solution, and organic sulphur source is then added into the first solution.
Using this kind of preferred embodiment, it is more advantageous to and is uniformly mixed molybdate compound with organic sulphur source.It is preferred that first solution
Preparation and the addition of organic sulphur source carry out under agitation so that tetrathiomolybdate is more filled with the contact of organic sulphur source
Divide, uniformly.The speed of stirring can be 10-500rpm.
There is no particular limitation for concentration of the present invention to first solution, in preferably described first solution, with Mo element
Meter, the concentration of molybdate compound are 0.2-0.5mol/L, further preferably 0.3-0.4mol/L.
In the present invention, under preferable case, the molybdate compound is selected from sodium molybdate, ammonium paramolybdate, ammonium phosphomolybdate and three oxygen
Change at least one of molybdenum, further preferably sodium molybdate and/or ammonium paramolybdate.When the molybdate compound is molybdenum trioxide
When, the invention also includes ammonium hydroxide or inorganic acid hydrotropy is introduced into the first solution, its introduction volume is not particularly limited.
The present invention is wider to the range of choice of the dosage of organic sulphur source and molybdate compound, as long as making in terms of element sulphur
Organic sulphur source and the molar ratio of the molybdate compound in terms of molybdenum element are not less than 4, preferably 4-6:1, further preferably
4-5.5:1.The reaction requirement of the two can either be met using this kind of preferred embodiment, and raw material can be efficiently used, do not made
At the wasting of resources.
Mixture obtained by step a) is reacted into 2-24h under the conditions of being 5-10 for 50-100 DEG C and/or pH, can both make O-
S exchange sufficiently carries out, in order to enable O-S exchange is more abundant, preferably reacts mixture obtained by step a) at 70-100 DEG C
2-24h, preferably reaction 10-16h, or pH be 5-6 under the conditions of react 2-24h, preferably reaction 3-7h, or pH be 8-10
Under the conditions of react 2-24h, preferably reaction 3-7h.It should be noted that under above-mentioned reaction temperature, if the reaction time is too short,
It is unfavorable for being fully hydrolyzed for organic sulphur source, and is unfavorable for the abundant progress of O-S exchange, sulphur source utilization rate reduces.
A preferred embodiment of the invention, the reaction carry out in confined conditions.It grasps in confined conditions
Make, the hydrogen sulfide that organic sulphur source hydrolyzes will not be discharged into air, neither will cause the pollution of air, and advantageously
It is hydrolyzed to sulfidion in hydrogen sulfide, it is more efficient to utilize sulphur source, more efficient processability preferably tetrathiomolybdate
Solution.
, according to the invention it is preferred to adjust pH by the way that acid and/or alkali are added into the mixture in step b), the acid can
To be organic acid, it is also possible to inorganic acid, there is no particular limitation to this by the present invention.
In accordance with the present invention it is preferred that sour at least one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid and acetic acid
Kind, further preferably hydrochloric acid.Using this kind of preferred embodiment, the impurity element being introduced into is in catalyst preparation late stage
Heat treatment or drying process in, naturally remove, will not influence the performance of catalyst.
In accordance with the present invention it is preferred that the alkali is selected from least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide, into one
Step is preferably sodium hydroxide.
A preferred embodiment of the invention, tetrathiomolybdate solution are made by following methods:
A) molybdate compound, organic sulphur source and water are mixed；
B) mixture obtained by step a) is reacted into 2-24h under the conditions of being 5-10 for 50-100 DEG C and/or pH；
Organic sulphur source can be the various sulphur-containing substances that can be hydrolyzed under the conditions of step (1) and/or step (2).
It is preferred that organic sulphur source is selected from thioamides shown in L- cysteine, formula (1), list monothioester and formula (3) shown in formula (2)
Shown at least one of dithioesters,
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 tert-butyl.R2And R3
It can be identical or different.
According to the present invention, organic sulphur source can hydrolyze to be various under the conditions of step (1) and/or step (2)
Sulphur-containing substance.It is preferred that organic sulphur source is selected from thioamides shown in L- cysteine, formula (1), list sulphur shown in formula (2)
For at least one of dithioesters shown in ester and formula (3),
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 tert-butyl.R2And R3
It can be identical or different.Further preferred organic sulphur source is thioamides shown in formula (1), still more preferably described to have
Machine sulphur source is thiocarbamide and/or thioacetamide, most preferably thioacetamide.
A preferred embodiment of the invention, the preparation method of hydrogenation catalyst provided by the invention include: a)
Molybdate compound, organic sulphur source and water are mixed；It b) is 5-10 condition at 50-100 DEG C and/or pH by mixture obtained by step a)
Lower reaction 2-24h；C) group VIII metal salt is added into the tetrathiomolybdate solution that step b) is obtained, it is molten to form mixing
Liquid impregnates carrier using the mixed solution, is then dried, obtains composite A；Or step b) is respectively adopted
The solution of obtained tetrathiomolybdate solution and the metal salt containing group VIII impregnates carrier, carries out after dipping every time
It is dry, obtain composite A；D) it under inert atmosphere or reducing atmosphere, is heat-treated, is heat-treated to composite A is obtained
So that Mo exists in the form of trisulfide in composite A；Wherein, organic sulphur source be can be in step a) and/or step
B) sulphur-containing substance hydrolyzed under the conditions of.
According to the present invention, before above-mentioned steps c), can also include the tetrathiomolybdate solution that is obtained to step b) into
Row concentration is perhaps diluted to 0.2-1.8mol/L further preferably concentration or dilution most 0.3-1.2mol/L.
The present invention is to the solution of group VIII metal salt in the solution of the mixed solution or the metal salt containing group VIII
Concentration is not particularly limited, it is preferable that the concentration of the solution of the group VIII metal salt is 0.1-1mol/L, further preferably
For 0.3-1mol/L.
In order to which a more step improves the Hydrogenation of hydrogenation catalyst, the preferably described tetrathiomolybdate, group VIII metal
The dosage of salt and carrier makes, and on the basis of the total amount of catalyst, the content of the carrier is 59-90 weight %, with oxidation
Object meter, the content of group VIII metallic element are that the content of 1-15 weight %, Mo are 5-40 weight %.It is further preferred that institute
The dosage for stating tetrathiomolybdate, group VIII metal salt and carrier makes, on the basis of the total amount of catalyst, the carrier
Content be 65-85 weight %, further preferably 71-84 weight %；In terms of oxide, the content of group VIII metallic element
For 1-10 weight %, further preferably 1.5-6 weight %；The content of Mo is 8-30 weight %, further preferably 10-23 weight
Measure %.
In the present invention, under preferable case, the group VIII metal salt is selected from nitrate, carbonate, the chlorine of cobalt and/or nickel
One of salt dissolving, sulfate and acetate are a variety of.
In the present invention, it is preferred to elemental metal, the additional amount and tetrathio molybdic acid of the group VIII metal salt
The molar ratio of salt is 0.1-1, preferably 0.2-0.5.It is relatively beneficial to play group VIII metal using this kind of preferred embodiment
With the synergistic effect of Mo, and it is relatively beneficial to the formation of active phase, while when carrying out reduction treatment to catalyst before going into operation, more had
Conducive to the full cure of Mo.
According to the present invention, in step (1), tetrathiomolybdate and group VIII metal salt are introduced by impregnating to carrier
During solution, the solid material after dipping is dried every time, and the present invention is not special to the condition of the drying
Restriction, can be various drying conditions commonly used in the art, for example, the condition of the drying include: temperature be 80-120 DEG C,
Time is 2-8h；Preferably, temperature is 80-100 DEG C, time 3-6h.The drying can carry out under air, but in order to true
Sulfide free of losses is protected, the preferably described drying carries out under an inert atmosphere.
According to the present invention, in step (2), the inert atmosphere can be by one of nitrogen, argon gas and helium or a variety of
It provides, is preferably provided by nitrogen.
According to the present invention, the reducing atmosphere can be by hydrogen and/or hydrogen sulfide and optionally inert gas offer.Institute
Inert gas can be contained by stating in reducing atmosphere, when containing inert gas in the reducing atmosphere, hydrogen and/or hydrogen sulfide
Volume content is not less than 5%.
In the present invention, the condition that composite A is heat-treated in step (2) must make in composite A Mo with
Trisulfide form exists, it is preferable that under inert atmosphere, the condition of the heat treatment includes: that temperature is 250-300 DEG C, the time
For 2-8h；Preferably, temperature is 260-270 DEG C, time 3-6h；Preferably, under reducing atmosphere, the condition packet of the heat treatment
Include: temperature is 200-250 DEG C, time 2-8h；Preferably, temperature is 200-230 DEG C, time 3-6h.
The temperature of the heat treatment can neither be too high, can not be too low, when heat treatment when the temperature is excessively high, it is easier that compound
Active metal component Mo directly exists with disulfide form in materials A, is unfavorable for the subsequent vulcanization for helping active component, also unfavorable
In the formation of II class activity phase, when the temperature of heat treatment is too low, it is unfavorable for the decomposition of tetrathiomolybdate.
The selection of the carrier does not require particularly, and such as carrier can be selected from gama-alumina, silica, oxidation
Aluminium-silica, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica thoria, silica-oxidation
Beryllium, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-oxidation
One of aluminium-titanium oxide, silicaalumina-magnesia and silica-alumina, zirconia are a variety of, no longer superfluous herein
It states.
There is no particular limitation to the dipping by the present invention, can be various dipping methods commonly used in the art, example
Such as incipient impregnation, details are not described herein.
The hydrogenation catalyst as made from above-mentioned preparation method have excellent hydrodesulfurization activity, therefore the present invention also provides
The hydrogenation catalyst as made from above-mentioned preparation method and its application in hydrodesulfurization.
The present invention also provides a kind of hydrogenation catalyst, catalyst any one of the above method provided by the present invention
It is prepared.The catalyst includes the active metal component of carrier and load on this carrier, which includes
Mo and at least one group VIII metallic element, Mo exist in the form of trisulfide, and the group VIII metallic element is with salt
Form exists.
In hydrogenation catalyst provided by the invention, Mo exists in the form of trisulfide, and group VIII metallic element is with salt
Form exists, it is only necessary to carry out simple reduction treatment to catalyst before going into operation, adjuvant component can be vulcanized (MoS3It is converted into
MoS2, group VIII metal salt is converted into the sulfide of group VIII metal), and obtain the II class Co with greater catalytic performance
(Ni)-Mo-S activity phase has preferable Hydrogenation.
In the present invention, the existing forms of Mo in hydrogenation catalyst can be measured by method of X-ray diffraction.MoS3In XRD
There are disperse peaks at 2 θ is 14.2 ° on map.In hydrogenation catalyst provided by the invention, the group VIII metallic element base
This exists in the form of group VIII metal active presoma, i.e., the described group VIII metallic element exists in a salt form, can
To be the salt for having the crystallization water, it is also possible to the salt of no crystal water.
Catalyst sulphidity with higher provided by the invention, it is preferable that described in being measured as X-ray electron spectrum
The sulphidity of catalyst is 96.5-99%.
In the present invention, unless otherwise specified, the sulphidity of the catalyst analyzes (XPS) by x-ray photoelectron spectroscopy
Measurement, wherein sulphidity is obtained by XPS data processing, and specific processing method can be found in document Han et al., Journal of
Materails Chemistry 2012,22:25340。
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
The content of standard, the carrier is 59-90 weight %, and in terms of oxide, the content of group VIII metallic element is 1-15 weight %,
The content of Mo is 5-40 weight %.
A preferred embodiment of the invention, on the basis of the total amount of catalyst, the content of the carrier is 65-
85 weight %, further preferably 71-84 weight %；In terms of oxide, the content of group VIII metallic element is 1-10 weight
Measure %, further preferably 1.5-6 weight %；The content of Mo is 8-30 weight %, further preferably 10-23 weight %.
Catalytic component content is all made of X-ray fluorescence spectra analysis method RIPP 132-90 (petrochemical analysis method
(RIPP experimental method), Yang Cuiding, Gu Kanying, Wu Wenhui are compiled, Science Press's nineteen ninety September first edition, the 371-379 pages)
It measures.
It should be noted that since active metal component exists in the form of sulfide and salt respectively, and above-mentioned metal group
Divide with the content meter of oxide.Obviously, when the catalyst only contains said components, the content of each component necessarily satisfying for
100%.
In the present invention, under preferable case, the group VIII metallic element is cobalt and/or nickel element.
There is no particular limitation for carrier of the present invention to the catalyst, can be porous oxide carrier, such as can be with
Selected from gama-alumina, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-magnesias, silica-zirconia,
Silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-
Alumina-thorias, silica-alumina-titania, silicaalumina-magnesia and silica-alumina, zirconia
One of or it is a variety of.The particularly preferred carrier is γ-Al of the diameter in 2mm to 5mm2O3Particle.Above-mentioned carrier can be commercially available
It obtains, can also be prepared using existing method.
Catalyst provided by the invention before use, do not need carry out presulfurization, when going into operation only need carry out simply also
Adjuvant component can be vulcanized (MoS by original place reason3It is converted into MoS2, group VIII metal salt is converted into the vulcanization of group VIII metal
Object), and obtain II class Co (the Ni)-Mo-S activity phase with greater catalytic performance.
Therefore, the present invention also provides a kind of methods of hydrofinishing, this method comprises: by hydrogenation catalyst provided by the invention
Agent is activated to obtain activation rear catalyst, under Hydrofinishing conditions, in presence of hydrogen, by hydrogen refined material to be added and institute
Activation rear catalyst is stated to be contacted.
The method of the hydrofinishing provided according to the present invention, it is preferable that the condition of the activation include: in inert atmosphere or
Under reducing atmosphere, temperature is 240-500 DEG C, time 1-12h；It is further preferred that under inert atmosphere or reducing atmosphere, In
Temperature is to activate 0.5-6h at 240-310 DEG C, activates 0.5-6h at being then 320-500 DEG C in temperature.The present inventor
It was found that first being activated under low temperature (240-310 DEG C) in activation process, then activates, be more advantageous under high temperature (320-500 DEG C)
The sulphidity and addition agent modified degree for improving activation rear catalyst are more advantageous to the hydrodesulfurization performance for improving catalyst.
A preferred embodiment of the invention, it is described activation rear catalyst sulphidity be 90-100% (preferably
For 95-99%), addition agent modified degree is 30-70% (preferably 40-60%).In the present invention, unless otherwise specified, described to urge
The sulphidity of agent is by x-ray photoelectron spectroscopy analysis (XPS) measurement, wherein sulphidity is obtained by XPS data processing, specifically
Processing method can be found in document Han et al., Journal of Materails Chemistry 2012,22:25340.
Heretofore described addition agent modified degree refers to the content of II class activity phase A-B-S of hydrogenation catalyst in catalyst, A
It represents group VIII metallic element (such as Co, Ni), B represents Mo element, and S is element sulphur.Hydrogenation catalyst after over cure
In, group VIII metallic element exists in different forms, and by taking Co as an example, in sulphided state CoMo catalyst, Co is respectively with Co2+、Co-
Mo-S and Co9S8Form exists, and existing Co corresponds to the peak of different location in XPS spectrum figure in different forms, by solving to peak
It is folded, calculate Co2+, Co-Mo-S and Co9S8Corresponding peak area corresponds to peak area/(Co by Co-Mo-S2+Corresponding peak area+
Co-Mo-S corresponds to peak area+Co9S8Corresponding peak area) × 100% content for calculating II class activity phase Co-Mo-S, this method is same
Sample is suitable for NiMo catalyst.Circular can be found in Qiu Limei article, and (X-ray photoelectron spectroscopy studies hydrodesulfurization
The chemical state [J] of active element in catalyst, petroleum journal: PETROLEUM PROCESSING, 2011,27 (4): 638-642).
Catalyst provided by the invention can be used for any required raw material for carrying out hydrofinishing, evaporate especially suitable for petroleum
The unifining process or weighted BMO spaces process of point oil or coal liquefaction fraction oil, it is preferable that the hydrogen refined material to be added is
Fraction oil of petroleum or coal liquefaction fraction oil.Part of the embodiment of the present invention is illustrated by taking gasoline, diesel oil model compound as an example, but
The present invention is not limited thereto.
Hydrofinishing process according to the present invention, the Hydrofinishing conditions can be conventional Hydrofinishing conditions.Example
Such as: temperature can be 200-425 DEG C, preferably 300-400 DEG C；Hydrogen partial pressure can be 1-15 megapascal, preferably 2-8 megapascal；Hydrogen
Oil volume ratio can be 100-5000, preferably 200-1000；Liquid hourly space velocity (LHSV) can be 0.2-5 hours-1, preferably 0.2-3 is small
When-1。
Below by way of the specific embodiment implementation process that the present invention will be described in detail and generated beneficial effect, it is intended to help
Where reader more clearly understands Spirit Essence of the invention, but any restriction cannot be constituted to practical range of the invention.
In following embodiment, Components of Catalysts content is all made of the measurement of X-ray fluorescence spectra (XRF) method, wherein X is penetrated
Line fluorescence spectrum (XRF) method uses ZSX-100e type Xray fluorescence spectrometer, using Rh target, in electric current 50mA, voltage 50kV's
Under the conditions of measure.
In catalyst the sulphidity of host agent Mo by x-ray photoelectron spectroscopy analysis (XPS) measurement, wherein sulphidity by
XPS data 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 light
It is carried out on electron spectrometer (Britain's VG Products), uses radiation source for Al K α, resolution ratio 0.5eV, be inside designated as pollution carbon
C1s combination can (Eb=285.0eV) condition obtain.
The existing forms of Mo are characterized by XRD (X-ray diffraction) in catalyst, and XRD spectra passes through Rigaku D/
3400 type x-ray diffractometer of Max is acquired；The scanning range of diffracting spectrum is 5-70 ° (2 θ), the use of radiation source is Cu K
α, 38 °/min of scanning speed.
Embodiment 1
(1) preparation of tetrathiomolybdate and nickel acetate mixed solution
(a) sodium molybdate is mixed with water, after stirring 40min, thioacetamide is added, stir 30min, preparation obtains 40mL
The solution of sodium molybdate, 1.75mol/L thioacetamide containing 0.35mol/L is heated to 95 DEG C of reactions under confined conditions
10h obtains tetrathiomolybdate solution；UV-Vis test, UV-Vis characterization knot are carried out to obtained tetrathiomolybdate solution
Fruit is as shown in Figure 1, peak shows MoS in solution at figure medium wavelength 260nm, 317nm and 468nm4 2-Presence；(b) according to Ni:Mo
Molar ratio weighs nickel acetate for 0.5, is added in above-mentioned solution and obtains mixed solution, then concentrates it to 8mL.
(2) preparation of hydrogenation catalyst
Using above-mentioned mixed solution solution to 10g diameter 2-5mm γ-Al2O3Carrier (specific surface area 231m2/ g, hole
Volume 0.709mL/g, similarly hereinafter) saturation dipping is carried out, dip time 4h dries 3h at 80 DEG C in a nitrogen atmosphere later,
Obtain composite A；Then composite A is heat-treated at lower 270 DEG C of nitrogen atmosphere, handles time 4h, is added
Hydrogen catalyst S-1.XRD characterization analysis is carried out to S-1, such as Fig. 2,2 θ are MoS occur at 14.2 ° as can be seen from Figure 23Feature
Disperse peak, it was demonstrated that molybdenum is in S-1 with MoS3Form exists, and under heat treatment condition, nickel salt is simultaneously undecomposed, in hydrogenation catalyst S-1
Nickel element exists in a salt form.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 2
(1) preparation of tetrathiomolybdate and nickel nitrate mixed solution
(a) ammonium paramolybdate is mixed with water, after stirring 40min, thioacetamide is added, stirs 30min, preparation obtains
Ammonium paramolybdate of the 30mL containing 0.045mol/L, 1.26mol/L thioacetamide solution be heated to 80 under confined conditions
DEG C reaction 16h, obtain tetrathiomolybdate solution, then concentrate it to 8mL；Obtained tetrathiomolybdate solution is carried out
UV-Vis test, UV-Vis characterization result is consistent with Fig. 1, equally has peak to be formed at figure medium wavelength 260nm, 317nm and 468nm,
Show MoS in solution4 2-Presence；(b) nickel nitrate is weighed for 0.3 according to Ni:Mo molar ratio, is added in above-mentioned solution and obtains
Then mixed solution concentrates it to 8mL.
(2) preparation of hydrogenation catalyst
Use above-mentioned mixed solution to 10g diameter for the γ-Al of 2-5mm2O3Carrier carries out saturation dipping, and dip time is
Then 4h dries 3h at 80 DEG C under an argon atmosphere, obtains composite A；Then to compound at lower 260 DEG C of nitrogen atmosphere
Materials A is heat-treated 6h, obtains hydrogenation catalyst S-2；XRD characterization analysis is carried out to S-2,2 θ are MoS occur at 14.2 °3Spy
Levy disperse peak, it was demonstrated that molybdenum is in S-2 with MoS3Form exists；And under heat treatment condition, nickel salt is simultaneously undecomposed, hydrogenation catalyst S-2
Middle nickel element exists in a salt form.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 3
(1) preparation of tetrathiomolybdate and nickel acetate mixed solution
(a) sodium molybdate is mixed with water, after stirring 40min, thioacetamide is added, stir 30min, preparation obtains 30mL
The solution of sodium molybdate, 1.75mol/L thioacetamide containing 0.35mol/L is heated to 70 DEG C of reactions under confined conditions
14h obtains tetrathiomolybdate solution, then concentrates it to 4mL；UV-Vis is carried out to obtained tetrathiomolybdate solution
Test, UV-Vis characterization result is consistent with Fig. 1, equally has peak to be formed at figure medium wavelength 260nm, 317nm and 468nm, shows molten
MoS in liquid4 2-Presence；(b) be 0.4 to weigh nickel acetate according to Ni:Mo molar ratio, be added in above-mentioned solution obtain mixing it is molten
Then liquid concentrates it to 4mL.
(2) preparation of hydrogenation catalyst
Use above-mentioned mixed solution to 10g diameter for the γ-Al of 2-5mm2O3Carrier carries out saturation dipping, and dip time is
Then 4h dries 3h at 80 DEG C in a nitrogen atmosphere, obtains composite A；Then to compound at lower 200 DEG C of hydrogen atmosphere
Materials A is heat-treated 3h, obtains hydrogenation catalyst S-3；XRD characterization analysis is carried out to hydrogenation catalyst S-3,2 θ are to go out at 14.2 °
Existing MoS3Feature disperse peak, it was demonstrated that molybdenum is in hydrogenation catalyst S-3 with MoS3Form exists；And under heat treatment condition, nickel salt is not
It decomposes, nickel element exists in a salt form in hydrogenation catalyst S-3.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 4
(1) preparation of tetrathiomolybdate and cobalt acetate mixed solution
(a) sodium molybdate is mixed with water, after stirring 40min, thioacetamide is added, the stirring and dissolving at 40 DEG C is prepared
It obtains the solution of sodium molybdate of the 30mL containing 0.4mol/L, 2mol/L thioacetyl, under stirring condition, 2.4M salt acid for adjusting pH is added dropwise
To 5-6,6h is reacted under confined conditions, obtains tetrathiomolybdate solution；UV- is carried out to obtained tetrathiomolybdate solution
Vis test, UV-Vis characterization result is consistent with Fig. 1, equally has peak to be formed at figure medium wavelength 260nm, 317nm and 468nm, shows
MoS in solution4 2-Presence；(b) cobalt acetate is weighed for 0.5 according to Co:Mo molar ratio, is added in above-mentioned solution and is mixed
Then solution concentrates it to 8mL.
(2) preparation of hydrogenation catalyst
Use above-mentioned mixed solution to 10g diameter for the γ-Al of 2-5mm2O3Carrier carries out saturation dipping, and dip time is
Then 4h dries 3h at 80 DEG C in a nitrogen atmosphere, obtains composite A；Then to compound at lower 270 DEG C of nitrogen atmosphere
Materials A is heat-treated 4h, obtains hydrogenation catalyst S-4；XRD characterization analysis is carried out to hydrogenation catalyst S-4,2 θ are to go out at 14.2 °
Existing MoS3Feature disperse peak, it was demonstrated that molybdenum is in S-4 with MoS3Form exists；And under heat treatment condition, cobalt salt is simultaneously undecomposed, adds hydrogen
Cobalt element exists in a salt form in catalyst S-4.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 5
(1) preparation of tetrathiomolybdate and cobalt acetate mixed solution
(a) sodium molybdate is mixed with water, after stirring 40min, thiocarbamide, the stirring and dissolving at 40 DEG C is added, preparation obtains
Sodium molybdate of the 30mL containing 0.35mol/L, 2mol/L thiocarbamide solution be heated to 70 DEG C of reaction 4h in confined conditions, add
Heat obtains tetrathiomolybdate solution to 97 DEG C of reaction 6h；UV-Vis test is carried out to obtained tetrathiomolybdate solution,
UV-Vis characterization result is consistent with Fig. 1, equally has peak to be formed at figure medium wavelength 260nm, 317nm and 468nm, shows in solution
MoS4 2-Presence；(b) be 0.5 to weigh cobalt acetate according to Co:Mo molar ratio, add it in above-mentioned solution obtain mixing it is molten
Then liquid concentrates it to 4mL；
(2) preparation of hydrogenation catalyst
Use above-mentioned mixed solution to 10g diameter for the γ-Al of 2-5mm2O3Carrier carries out saturation dipping, and dip time is
Then 4h dries 3h at 80 DEG C under an argon atmosphere, obtains composite A；Then to compound at lower 270 DEG C of nitrogen atmosphere
Materials A is heat-treated 4h, obtains hydrogenation catalyst S-5；XRD characterization analysis is carried out to hydrogenation catalyst S-5,2 θ are to go out at 14.2 °
Existing MoS3Feature disperse peak, it was demonstrated that molybdenum is in S-5 with MoS3Form exists；And under heat treatment condition, cobalt salt is simultaneously undecomposed, adds hydrogen
Cobalt element exists in a salt form in catalyst S-5.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 6
According to the method for embodiment 1, unlike, in the preparation process of tetrathiomolybdate solution, the reaction is being opened
It puts in environment and carries out.Obtain hydrogenation catalyst S-6.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 7
According to the method for embodiment 1, unlike, the additional amount of nickel is changed to be 0.1 preparation 7mL according to Ni:Mo molar ratio
Nickel acetate solution.Obtain hydrogenation catalyst S-7.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 8
According to the method for embodiment 1, unlike, in the preparation process of tetrathiomolybdate solution, shown reaction is 60
16h is carried out at DEG C.Obtain hydrogenation catalyst S-8.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 9
According to the method for embodiment 1, unlike, in the preparation process of hydrogenation catalyst, the temperature of heat treatment is 250
℃.Obtain hydrogenation catalyst S-9.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 10
According to the method for embodiment 1, unlike, in the preparation process of hydrogenation catalyst, the temperature of heat treatment is 280
℃.Obtain hydrogenation catalyst S-10.The results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 11
According to the method for embodiment 4, the difference is that, in step (1), it is 2mol/L's that hydrochloric acid is not added dropwise but concentration is added dropwise
NaOH solution adjusts pH to 9-9.5, obtains tetrathiomolybdate solution, then concentrates it to 8mL.Obtain hydrogenation catalyst S-
11, the results are shown in Table 1 for Components of Catalysts content analysis.
Embodiment 12
Tetrathiomolybdate solution is prepared according to the material investment of embodiment 1,8mL is concentrated into, then according to embodiment 1
Dosage weighs nickel acetate, is configured to 8mL nickel acetate solution.By 10g diameter 2-5mm γ-Al2O3Carrier successively uses above-mentioned four
Thiomolybdate solution and nickel acetate solution saturation dipping, each dip time be 4h, every time dipping after in a nitrogen atmosphere in
Dry 3h, obtains composite A at 80 DEG C；Then 4h is heat-treated to composite A at lower 270 DEG C of nitrogen atmosphere, is added
Hydrogen catalyst S-12；XRD characterization analysis is carried out to hydrogenation catalyst S-12,2 θ are MoS occur at 14.2 °3Feature disperse peak,
Prove that molybdenum is in catalyst S-12 with MoS3Form exists.And under heat treatment condition, nickel salt is simultaneously undecomposed, in hydrogenation catalyst S-12
Nickel element exists in a salt form.The results are shown in Table 1 for Components of Catalysts content analysis.
Above-mentioned catalyst before use, do not need carry out presulfurization, only need to carry out simple reduction treatment i.e. when going into operation
It can.Reduction treatment, the condition of reduction treatment are carried out to above-mentioned catalyst S-1 to S-12 are as follows: under hydrogen atmosphere, at 300 DEG C also
Former 3h.The sulphidity of treated catalyst is tested, test result is listed in Table 1 below.
Comparative example 1
Weigh the sodium molybdate, nickel acetate and γ-Al of amount in the same manner as in Example 12O3Carrier, using saturation step impregnation
Method prepares oxidation catalyst.Specifically: sodium molybdate is dissolved in 8mL deionized water, is made into maceration extract, impregnated carrier 2h, so
It places in baking oven in 120 DEG C of dry 3h afterwards, 400 DEG C of roasting 3h is warming up to the rate of 3 DEG C/min, obtain Mo/Al2O3；By acetic acid
Nickel is formulated as the maceration extract of 7mL, and saturation is impregnated in Mo/Al2O3, dip time 4h, then in 120 DEG C of dryings in placement baking oven
3h is warming up to 400 DEG C of roasting 3h with the rate of 3 DEG C/min, obtains NiMo/ γ-Al2O3, then take 1g NiMo/ γ-Al2O3Dress
" in device " vulcanization, conditions of vulcanization are as follows: conditions of vulcanization are as follows: pressure 4.0MPa, hydrogen to oil volume ratio are carried out into miniature hydrogenator
1800, sulfurized oil oil inlet flow is 8mL/h, and vulcanization temperature program is to be warming up to 230 DEG C with the heating rate of 10 DEG C/min, constant temperature
1h is warming up to 320 DEG C with the heating rate of 10 DEG C/min, is then warming up to 360 DEG C with the heating rate of 1 DEG C/min, at 360 DEG C
Constant temperature 105min obtains catalyst D-1 after vulcanization.The results are shown in Table 1 for Components of Catalysts content and sulphidity analysis.
Comparative example 2
Weigh the sodium molybdate, cobalt acetate and γ-Al of amount in the same manner as in Example 52O3Carrier, using saturation step impregnation
Method prepares oxidation catalyst.Detailed process obtains catalyst D- with comparative example 1 with comparative example 1, sulfidation after vulcanization
2.The results are shown in Table 1 for Components of Catalysts content and sulphidity analysis.
Comparative example 3
Sodium molybdate is mixed with water, after stirring 40min, thioacetamide is added, stirs 30min, preparation obtains 40mL and contains
The solution of the sodium molybdate of 0.35mol/L, 1.75mol/L thioacetamide, by it with 10g diameter in the γ-Al of 2-5mm2O3Carrier
It is transferred in autoclave, autoclave is then heated to 95 DEG C, react 10h, then by suspension filtering, washing, in nitrogen gas
3h is dried under atmosphere at 80 DEG C, then 4h is heat-treated at lower 270 DEG C of nitrogen atmosphere, obtains MoS2/γ-Al2O3, according to Ni:Mo
Molar ratio is 0.5 nickel acetate solution for preparing 7mL, and saturation is impregnated in MoS2/γ-Al2O3, dip time 4h, then in nitrogen
3h is dried under atmosphere at 100 DEG C, obtains hydrogenation catalyst D-3.Reduction treatment, reduction treatment are carried out to above-mentioned catalyst D-3
Condition are as follows: under hydrogen atmosphere, restore 3h at 300 DEG C.The sulphidity of treated catalyst is tested, test result
It is listed in Table 1 below.
Table 1
| Embodiment | Number | Metal composition | MoO3Quality % | NiO (CoO) quality % | Mo sulphidity % |
| 1 | S-1 | NiMo | 15.85 | 3.85 | 97.6 |
| Comparative example 1 | D-1 | NiMo | 15.87 | 3.83 | 70.4 |
| 2 | S-2 | NiMo | 12.43 | 1.75 | 96.7 |
| 3 | S-3 | NiMo | 22.17 | 4.56 | 97.9 |
| 4 | S-4 | CoMo | 12.55 | 3.28 | 98.3 |
| 5 | S-5 | CoMo | 22.37 | 5.85 | 96.9 |
| Comparative example 2 | D-2 | CoMo | 21.94 | 5.42 | 71.2 |
| 6 | S-6 | NiMo | 15.55 | 3.56 | 77.8 |
| 7 | S-7 | NiMo | 15.84 | 0.53 | 97.5 |
| Comparative example 3 | D-3 | NiMo | 7.85 | 1.26 | 69.8 |
| 8 | S-8 | NiMo | 15.66 | 3.52 | 92.7 |
| 9 | S-9 | NiMo | 15.84 | 3.86 | 97.5 |
| 10 | S-10 | NiMo | 15.82 | 3.84 | 97.6 |
| 11 | S-11 | CoMo | 15.79 | 3.82 | 98.0 |
| 12 | S-12 | NiMo | 15.82 | 3.82 | 97.4 |
Test example
In this test example, add to what the hydrogenation catalyst and comparative example using method provided by the present invention preparation provided
The desulphurizing activated of hydrogen catalyst is evaluated in accordance with the following methods, and lists result.
Hydrodesulfurization: with the n-decane solution of 4,6- dimethyl Dibenzothiophene (4,6-DMDBT) mass content 0.45%
For raw material, evaluates and urge on the continuous high pressure reaction assembly of MERYER-07054 of Mai Ruier experimental facilities Shanghai Co., Ltd production
Agent (D-1 and D-2 after S-1 to S-11 and D-3, vulcanizing treatment after reduction treatment) it is desulphurizing activated.Reaction condition are as follows:
4.0MPa, 300 DEG C, hydrogen to oil volume ratio 500, oil inlet flow is 8mL/h.It is sampled after stable reaction 2h, sample Agilent 7890A
Gas-chromatography is analyzed, and activity is indicated with the desulfurization degree of 4,6-DMDBT, the results are shown in Table 2.
Reaction desulfuration rate X is calculated as follows:
X=(feedstock oil sulfur content-product oil sulfur content)/feedstock oil sulfur content × 100%
Table 2
| Embodiment | Number | Metal composition | Desulfurization degree % |
| 1 | S-1 | NiMo | 99.8 |
| Comparative example 1 | D-1 | NiMo | 93.2 |
| 2 | S-2 | NiMo | 99.7 |
| 3 | S-3 | NiMo | 99.8 |
| 4 | S-4 | CoMo | 99.8 |
| 5 | S-5 | CoMo | 99.9 |
| 6 | S-6 | NiMo | 95.3 |
| 7 | S-7 | NiMo | 89.3 |
| Comparative example 3 | D-3 | NiMo | 87.4 |
| 8 | S-8 | NiMo | 97.5 |
| 9 | S-9 | NiMo | 98.7 |
| 10 | S-10 | NiMo | 97.5 |
| 11 | S-11 | CoMo | 99.7 |
| 12 | S-12 | NiMo | 99.7 |
It can be illustrated by the result of table 1, table 2, compared with the hydrogenation catalyst of conventional method preparation, provided by the invention plus hydrogen
Catalyst may make main active component almost all to vulcanize, substantially increases active metal by simple reduction treatment
Utilization rate, although two class catalyst composition is similar, catalyst provided by the invention is with higher desulphurizing activated.The above results
Sufficiently show the superiority that the preparation method of hydrogenation catalyst provided by the present invention has conventional impregnation method incomparable.Separately
Outside, it under preferable case, using homemade tetrathiomolybdate solution as maceration extract, eliminates and tetrathiomolybdate solution is mentioned
The process of pure crystallization and tetrathiomolybdate dissolution, solves in the prior art, sulfurized hydrogenation catalyst production cost is higher
Defect.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
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 also be regarded as the disclosure of the present invention.
Claims (14)
1. a kind of preparation method of hydrogenation catalyst, includes the following steps:
(1) tetrathiomolybdate and group VIII metal salt are introduced on carrier, obtain composite A；
(2) composite A is heat-treated under inert atmosphere or reducing atmosphere, the heat treatment is so that in composite A
Mo exists in the form of trisulfide, and group VIII metallic element exists in a salt form.
2. according to the method described in claim 1, tetrathiomolybdate and group VIII metal salt are introduced described in step (1)
Method on to carrier are as follows: prepare tetrathiomolybdate solution, add group VIII metal salt thereto and form mixed solution, adopt
Carrier is impregnated with the mixed solution, is then dried；Or tetrathiomolybdate solution is respectively adopted and containing the
The solution of group VIII metal salt impregnates carrier, is dried after dipping every time.
3. preparation method according to claim 2, wherein the tetrathiomolybdate solution is made by following methods:
A) molybdate compound, organic sulphur source and water are mixed；
B) mixture obtained by step a) is reacted into 2-24h under the conditions of being 5-10 for 50-100 DEG C and/or pH；Organic sulphur source is
The sulphur-containing substance that can be hydrolyzed under the conditions of step a) and/or step b)；
Preferably, the concentration of the tetrathiomolybdate solution is 0.2-1.8mol/L, further preferably 0.3-1.2mol/L.
4. preparation method according to claim 3, wherein
Step a) the mixing includes: that molybdate compound is dissolved in water to form the first solution, and being then added into the first solution has
Machine sulphur source；
Preferably, in first solution, in terms of Mo element, the concentration of molybdate compound is 0.2-0.5mol/L；
Preferably, organic sulphur source in terms of element sulphur and the molar ratio of the molybdate compound in terms of molybdenum element are 4-6:1.
5. preparation method according to claim 3 or 4, wherein react mixture obtained by step a) at 70-100 DEG C
2-24h, preferably reaction 10-16h, or
2-24h is reacted under the conditions of pH is 5-6, preferably reaction 3-7h, or
2-24h is reacted under the conditions of pH is 8-10, preferably reaction 3-7h；
Preferably, the reaction carries out in confined conditions.
6. the preparation method according to any one of claim 3-5, wherein by into the mixture in step b)
Acid is added and/or alkali adjusts pH；Preferably, sour at least one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid and acetic acid
Kind, preferably hydrochloric acid；The alkali is selected from least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide, preferably sodium hydroxide.
7. the preparation method according to any one of claim 3-6, wherein the molybdate compound be selected from sodium molybdate,
At least one of ammonium paramolybdate, ammonium phosphomolybdate and molybdenum trioxide；
Organic sulphur source is selected from thioamides shown in L- cysteine, formula (1), list monothioester and formula (3) shown in formula (2)
Shown at least one of dithioesters,
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, organic sulphur source is thioamides, further preferably thiocarbamide and/or thioacetamide shown in formula (1),
Most preferably thioacetamide.
8. the preparation method according to any one of claim 2-7, wherein the mixed solution is golden containing group VIII
The concentration for belonging to group VIII metal salt in the solution of salt is 0.1-1mol/L；
Preferably, the dosage of the tetrathiomolybdate, group VIII metal salt and carrier makes, and is with the total amount of catalyst
The content of benchmark, the carrier is 59-90 weight %, and in terms of oxide, the content of group VIII metallic element is 1-15 weight
% is measured, the content of Mo is 5-40 weight %；
Preferably, the group VIII metal salt is selected from nitrate, carbonate, chlorate, sulfate and the acetic acid of cobalt and/or nickel
One of salt is a variety of.
9. preparation method described in any one of -8 according to claim 1, wherein with elemental metal, the group VIII
The dosage of metal salt and the molar ratio of tetrathiomolybdate are 0.1-1, preferably 0.2-0.5.
10. the preparation method according to any one of claim 2-9, wherein in step (1), the condition of the drying
Include: temperature be 80-120 DEG C, time 2-8h；Preferably, temperature is 80-100 DEG C, time 3-6h.
11. the preparation method according to any one of claim 2-10, wherein in step (2), the inert atmosphere by
One of nitrogen, argon gas and helium or a variety of offers, the reducing atmosphere is by hydrogen and/or hydrogen sulfide and optionally inertia
Gas provides；
Under inert atmosphere, the condition of the heat treatment includes: that temperature is 250-300 DEG C, time 2-8h；Preferably, temperature is
260-270 DEG C, time 3-6h；
Under reducing atmosphere, the condition of the heat treatment includes: that temperature is 200-250 DEG C, time 2-8h；Preferably, temperature is
200-230 DEG C, time 3-6h.
12. preparation method described in any one of -11 according to claim 1, wherein the carrier is selected from gama-alumina, oxygen
SiClx, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica thoria, oxygen
SiClx-beryllium oxide, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, oxygen
One of SiClx-aluminium oxide-titanium oxide, silicaalumina-magnesia and silica-alumina, zirconia are a variety of.
13. hydrogenation catalyst made from the preparation method as described in any one of claim 1-12.
14. application of the hydrogenation catalyst described in claim 13 in hydrodesulfurization.
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