CN110479313A - Hydrogenation catalyst and its preparation method and application and the method for hydrofinishing - Google Patents
Hydrogenation catalyst and its preparation method and application and the method for hydrofinishing Download PDFInfo
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- CN110479313A CN110479313A CN201810464234.XA CN201810464234A CN110479313A CN 110479313 A CN110479313 A CN 110479313A CN 201810464234 A CN201810464234 A CN 201810464234A CN 110479313 A CN110479313 A CN 110479313A
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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
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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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- General Chemical & Material Sciences (AREA)
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Abstract
The present invention relates to field of hydrogenation, disclose the method for a kind of hydrogenation catalyst and its preparation method and application and hydrofinishing, the catalyst includes the active metal component B of carrier and load on this carrier, amount of activated metal component B exists in the form of trisulfide, remainder active metal component B exists in the form of trioxide, the atomic ratio of sulphur and active metal component B are 2.1-2.9, and the sulphidity of catalyst is 40-80%.The method for preparing catalyst includes: to be impregnated using the solution C containing vib metals compound to carrier, is dried to obtain solid A；Solution D containing organic sulphur source is contacted with solid A, then obtained solid product is dried.Hydrogenation catalyst provided by the invention has excellent hydrogenation reaction activity, while can save the vulcanization start-up process of conventional hydrogenation catalyst, reduces on-stream time and saving goes into operation cost.
Description
Technical field
The present invention relates to field of hydrogenation, and in particular to hydrogenation catalyst and its preparation method and application and hydrofinishing
Method.
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.
In conventional fabrication techniques oxidized catalyst is first packed by pre-vulcanization process using " in device " sulfurization technology
In hydrogenator, hydrogen then is passed through into reactor during continuous heating and vulcanizing agent is vulcanized, although this
Technology is still the technology being most widely used at present, but it still remains a series of problems: 1) vulcanization time is too long, and delay is opened
Work；2) sulfidation easily causes corrosion of equipment, aging；3) vulcanizing agent is inflammable, toxic, easily pollutes the environment；4) cost
It is higher 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 devices "
Sulfurization technology, such technology mainly includes two lines: the first technology path is that first by vulcanizing agent, (elementary sulfur, has vegetable oil
Machine sulfide, organic polysulfide, sulfone and sulfoxide etc.) use distillation, melting or the method impregnated to be introduced into adding for oxidation state
It is then thermally treated in the presence of an inert gas to make catalyst vulcanization in the gap of hydrogen catalyst；Second of technology path be
In special prevulcanisation-devices, oxidized catalyst is completed in the presence of hydrogen and hydrogen sulfide or labile organic sulfurizing agent
Presulfurization.However, the catalyst that above-mentioned route obtains before being filled to reaction unit, need to be passivated processing, transport
The problem of there are the security risk of spontaneous combustion and Oxidative inactivations in journey, while needing special prevulcanisation-devices, prevulcanisation-devices
Build and can bring huge capital investment and potential environmental protection pressure and policy risk.
To realize the excellent Hydrogenation of hydrogenation catalyst, while vulcanization and " outside device " " in device " being avoided to vulcanize on existing
Problems are stated, the direct preparation route of sulphided state hydrogenation catalyst had obtained more and more concerns and exploration in recent years.Cause
This, above-mentioned technology path uses limitation and certain social risk there are still biggish at present.
Summary of the invention
The purpose of the invention is to overcome defect existing for existing " in device " vulcanization and " outside device " sulfurization technology, one is provided
The new hydrogenation catalyst of kind, the preparation method of hydrogenation catalyst and the hydrogenation catalyst as made from the preparation method, above-mentioned plus hydrogen
Application and a kind of method of hydrofinishing of the catalyst in hydrofinishing.Using made from preparation method provided by the invention
Hydrogenation catalyst has excellent hydrogenation reaction activity, while can save the vulcanization start-up process of conventional hydrogenation catalyst, reduces
On-stream time and saving go into operation cost.
First aspect present invention provides a kind of hydrogenation catalyst, which includes the work of carrier and load on this carrier
Property metal component B, active metal component B is selected from least one of vib metals element, amount of activated metal component B
Exist in the form of trisulfide, remainder active metal component B exists in the form of trioxide, by x-ray photoelectron spectroscopy
In the catalyst measured, the atomic ratio of sulphur and active metal component B are 2.1-2.9, and the sulphidity of catalyst is 40-80%
Second aspect of the present invention provides a kind of preparation method of hydrogenation catalyst, this method comprises:
(1) carrier is impregnated using the solution C containing vib metals compound, is dried to obtain solid A；
(2) solution D containing at least one organic sulphur source is contacted with solid A, then obtained solid product is carried out
It is dry；
Organic sulphur source is the sulphur-containing substance that can be hydrolyzed in solution D and/or under contact conditions, the temperature of the contact
Degree is 20-150 DEG C, and the time is not less than 0.5 hour.
Preferably, this method further includes pass-through mode 1) and/or mode 2) group VIII gold is introduced into hydrogenation catalyst
Belong to element；Mode 1) it include: the addition group VIII metallic compound into solution C；Mode 2) it include: to use to contain group VIII
The substance that the solution E of metallic compound is dried to obtain step (2) impregnates.
Third aspect present invention provides the hydrogenation catalyst as made from above-mentioned preparation method.
Fourth aspect present invention provides application of the above-mentioned hydrogenation catalyst in hydrofinishing.
Fifth aspect present invention provides a kind of method of hydrofinishing, this method comprises: provided by the invention plus hydrogen is urged
Agent is activated to obtain activation rear catalyst, under Hydrofinishing conditions, in presence of hydrogen, by hydrogen refined material to be added with
The activation rear catalyst is contacted.
The present inventor passes through the study found that during preparing hydrogenation catalyst, first uses containing group VIB gold
The solution C for belonging to compound impregnates carrier, is dried to obtain solid A, then using molten containing at least one organic sulphur source
Liquid D and solid A (temperature is 20-150 DEG C, and the time is not less than 0.5 hour) contact under certain condition, can be by most oxygen
Change state active material and be converted into sulphided state species, the oxygen sulphur in aqueous solution exchanges the hydrogenation catalyst of available suitable sulphidity
Agent, and after being handled by subsequent activation, the sulphided state catalyst of suitable sulphidity and higher addition agent modified degree can be obtained, is used for
In hydrogenation reaction, there is stronger activity.It, can be by the way that group VIII metallic compound be added into solution C under preferable case
And/or in such a way that the substance that the solution E containing group VIII metallic compound is dried to obtain step (2) impregnates to
Group VIII metallic element is introduced in catalyst, further increases the activity of catalyst.
The sulphided state hydrogenation catalyst obtained using existing " in device " vulcanization and " outside device " sulfurization technology, active metal and load
The active force of body is larger, and active metal sulphidity and addition agent modified degree are all lower, and catalyst activity is weaker.And use the prior art
The sulphided state hydrogenation catalyst that disclosed chemical deposition is prepared, measures on one side metal smaller, i.e., metal utilization is small
(high production cost), another prior aspect are that the active force of active metal and carrier is smaller, and catalyst stability is poor.
Oxidized catalyst is made using conventional impregnation method in method provided by the invention, then and containing at least one organic
The solution D of sulphur source is reacted, and amount is 100% on metal, lower production costs, and part active metal in obtained hydrogenation catalyst
Component B exists in the form of trioxide, and remainder active metal component B exists in the form of trisulfide, sulphur and active metal
The atomic ratio of component B is 2.1-2.9, and the sulphidity of catalyst is 40-80%, and the sulphidity of the catalyst is moderate, with carrier
Binding force is suitable, and the activation back end hydrogenation catalyst obtained after being activated to the catalyst has suitable sulphidity.When
In catalyst preparation process, when also introducing group VIII metallic element, the activation back end hydrogenation catalyst obtained after activation processing has
There is higher addition agent modified degree, when being used for hydrotreating, there is more high activity.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
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.
First aspect present invention provides a kind of hydrogenation catalyst, which includes the work of carrier and load on this carrier
Property metal component B, active metal component B is selected from least one of vib metals element, amount of activated metal component B
Exist in the form of trisulfide, remainder active metal component B exists in the form of trioxide, by x-ray photoelectron spectroscopy
In the catalyst measured, the atomic ratio of sulphur and active metal component B are 2.1-2.9, and the sulphidity of catalyst is 40-80%
In hydrogenation catalyst provided by the invention, active metal component B is deposited in the form of trioxide and two kinds of trisulfide
And the atomic ratio of sulphur and active metal component B are 2.1-2.9, and the sulphidity of catalyst is moderate, it is only necessary to urging before going into operation
Agent is simply activated, and can have preferable Hydrogenation.
In the present invention, in the form of trioxide existing for active metal component B and in the form of trisulfide existing for activity
The ratio of metal component B can be calculated according to the specific value of sulphur and the atomic ratio of active metal component B.
In the present invention, under preferable case, active metal component B is molybdenum and/or wolfram element.
There is no particular limitation to the carrier by the present invention, can be various carriers commonly used in the art, can be commercially available
Commodity can also be prepared by any one method in the prior art, can be porous oxide carrier, such as γ-oxygen can be selected from
Change aluminium, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica-oxygen
Change thorium, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-oxygen
Change one of thorium, silica-alumina-titania, silicaalumina-magnesia and silica-alumina, zirconia
Or it is a variety of.The particularly preferred carrier is γ-Al of the diameter in 1mm to 5mm2O3Particle.
In the present invention, active metal component B in hydrogenation catalyst can be measured by x-ray photoelectron spectroscopy (XPS)
Existing forms.
In the present invention, under the conditions of no specified otherwise, x-ray photoelectron spectroscopy analyzes (XPS) in ESCALab 250 model X
It is carried out on X-ray photoelectron spectroscopy X instrument (Britain's VG Products), radiation source is used inside to be designated as Al K α, resolution ratio 0.5eV
The condition for polluting the combination energy (Eb=285.0eV) of the C1s of carbon obtains.
In the present invention, the atomic ratio of sulphur and active metal component B is given also by x-ray photoelectron spectroscopy analysis result
Out.
In the present invention, the sulphidity of catalyst is by x-ray photoelectron spectroscopy analysis (XPS) measurement, wherein sulphidity
It is obtained by XPS data processing, specific processing method can be found in document Han et al., Journal of Materials
Chemistry 2012,22:25340。
The atomic ratio of a preferred embodiment of the invention, sulphur and active metal component B are 2.5-2.8.This kind
Preferred embodiment is more advantageous to the catalytic performance for improving catalyst.
A preferred embodiment of the invention, the sulphidity of the hydrogenation catalyst are 60-85%, preferably 65-
72%.This kind of preferred sulphidity is more suitable for being better able to take into account the activity of catalyst and stability.The vulcanization of hydrogenation catalyst
Degree is the ratio for criticizing the total active metal component B of active metal component B Zhan of tetravalence.Although amount of activated metal component B with
Trisulfide form exists, but there are S in catalyst2 2-, therefore there are positive tetravalences to be deposited in the form of trisulfide in hydrogenation catalyst
Active metal component B.
A preferred embodiment of the invention, the hydrogenation catalyst is after being activated, sulphidity 65-
90%, preferably 70-90%, more preferably 80-89%；
It is 1h that the condition of the activation processing, which includes: in hydrogen gas space velocity,-1, under conditions of hydrogen partial pressure is 4MPa, at 250 DEG C
Reason 2 hours then heats to 360 DEG C and handles 4 hours.
Hydrogenation catalyst provided by the invention is activated under specific activation condition, suitable sulphur can be obtained
(the sulphided state hydrogenation catalyst sulphidity relatively obtained using existing " in device " vulcanization and " outside device " sulfurization technology is high, relatively adopts for change degree
The sulphidity for the sulphided state hydrogenation catalyst that the chemical deposition disclosed in the prior art is prepared is low), than existing offer
Sulphided state hydrogenation catalyst is compared, and has higher catalyst activity.
Catalyst vulcanization degree test method after being activated as described above, do not repeating herein.
A preferred embodiment of the invention, on the basis of the total amount of catalyst, the content of carrier is 60-90 weight
%, preferably 70-85 weight % are measured, in terms of oxide, the content of active metal component B is 10-40 weight %, preferably 15-
30 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.
Above-mentioned catalyst is monometallic hydrogenation catalyst, in order to further improve the Hydrogenation of catalyst, it is preferable that
The catalyst further includes the active metal component A being supported on carrier, and active metal component A is selected from group VIII metallic element
At least one of.
In the present invention, under preferable case, the active metal component A is cobalt and/or nickel element.
A preferred embodiment of the invention, after being activated, addition agent modified degree is the hydrogenation catalyst
28-60%, preferably 35-52%, further preferably 43-50%, the addition agent modified degree refer to through X-ray electronics energy
Compose the active metal component A that measures in the form of II class activity phase A-B-S existing for amount and active metal component A total amount ratio,
The condition of the activation processing is as described above, details are not described herein.
Heretofore described addition agent modified degree refers to the content of II class activity phase A-B-S in catalyst, that is, passes through X-ray
The active metal component A that electron spectrum measures in the form of II class activity phase A-B-S existing for amount with active metal component A total amount
Ratio.A is represented group VIII metallic element (such as Co, Ni), and B is represented vib metals element (such as Mo, W), and S is sulphur member
Element.In hydrogenation catalyst after being activated, group VIII metallic element exists in different forms, by taking Co as an example, vulcanization
In state CoMo catalyst, Co is respectively with Co2+, Co-Mo-S and Co9S8Form exists, and existing Co corresponds to XPS spectrum in different forms
The peak of different location in figure is folded by carrying out solution to peak, calculates Co2+, Co-Mo-S and Co9S8Corresponding peak area, passes through
Co-Mo-S corresponds to peak area/(Co2+The corresponding corresponding peak area+Co of peak area+Co-Mo-S9S8Corresponding peak area) × 100% meter
The content of II class activity phase Co-Mo-S is calculated, this method is equally applicable to NiW catalyst.Circular can be found in Qiu Limei
(X-ray photoelectron spectroscopy studies the chemical state [J] of active element in Hydrobon catalyst to article, and petroleum journal: petroleum adds
Work, 2011,27 (4): 638-642).
A preferred embodiment of the invention, on the basis of the total amount of catalyst, the content of carrier is 54-85 weight
% is measured, in terms of oxide, the content of active metal component A is 1-10 weight %, and the content of active metal component B is 8-45 weight
Measure %；It is further preferred that the content of carrier is 68-84 weight % on the basis of the total amount of catalyst, it is living in terms of oxide
Property metal component A content be 1.5-6 weight %, the content of active metal component B is 10-30 weight %.
It should be noted that since active metal component exists in the form of oxide and sulfide respectively, and above-mentioned gold
Belong to component with the content meter of oxide.Obviously, when the catalyst only contains said components, the content of each component is inevitable
Meet 100%.
Second aspect of the present invention provides a kind of preparation method of hydrogenation catalyst, this method comprises:
(1) carrier is impregnated using the solution C containing vib metals compound, is dried to obtain solid A；
(2) solution D containing at least one organic sulphur source is contacted with solid A, then obtained solid product is carried out
It is dry；
Organic sulphur source is the sulphur-containing substance that can be hydrolyzed in solution D and/or under contact conditions, the temperature of the contact
Degree is 20-150 DEG C, and the time is not less than 0.5 hour (preferably 0.5-40 hours).
Method provided by the invention in the solution, by organic sulphur source and solid A (temperature 20-150 under given conditions
DEG C, the time is not less than 0.5 hour) contact, organic sulphur source hydrolysis generation H2S or S2-, and then react and be formed in situ with solid A
The active specy of sulphided state.This method is easy to operate, in obtained hydrogenation catalyst vib metal quite a few with trisulfide
Form exist, subsequent activation processing is carried out to it, will form the group vib metal disulfides with abundant lattice defect position.
The present inventor has found that the trisulfide is very beneficial for auxiliary agent to the dynamic transition process of disulphide by research again
Modification of the group VIII metallic atom to it advantageously forms II class activity phase A-B-S abundant.
A preferred embodiment of the invention, vib metals element are molybdenum and/or wolfram element.The Section VI B
Race's metallic compound can selected from molybdenum trioxide, tungstic acid, ammonium molybdate, sodium molybdate, sodium tungstate, ammonium tungstate, metamolybdic acid ammonium, partially
At least one of ammonium tungstate, ammonium phosphomolybdate and ammonium phosphotungstate.
The selection of the carrier is as described above, details are not described herein.When vib metals compound is selected from molybdenum trioxide
And/or when tungstic acid, cosolvent, such as phosphoric acid can also be contained in solution C, about the dosage of cosolvent, art technology
Personnel can select according to the actual situation, as long as molybdenum trioxide and/or tungstic acid is enabled to sufficiently to dissolve.
The present invention is wider to the dosage range of choice of vib metals compound and carrier, it is preferable that vib metals
The dosage of compound and carrier makes, and in catalyst obtained, on the basis of the total amount of catalyst, the content of carrier is 60-90
Weight %, preferably 70-85 weight %, in terms of oxide, the content of vib metals element is 10-40 weight %, preferably
15-30 weight %.
Step (1) the of the present invention dipping can be saturation dipping.Solvent in solution C can be water, wherein group VIB
The concentration of metallic compound can be selected according to the water absorption rate of carrier and the amount for the vib metals compound to be loaded
It selects, details are not described herein by the present invention.
The present invention restriction no to the item of step (1) described drying, can be by the interior condition being widely used of industry, example
It is 1-6 hours dry at 80 DEG C -150 DEG C such as in air atmosphere.
According to the present invention, the solid A is without roasting.And oxidized catalyst described in the prior art refer generally to through
Catalyst after crossing roasting.
A preferred embodiment of the invention, the pH of the solution D are 3.5-6.5 or 7.5-10.5.The present invention
This kind of preferred embodiment in, solution D is under more mild acidity or alkaline condition, so guarantee carrier do not broken
Promote transformation of the solid A to sulphided state active specy in the case where bad.When the pH value of solution D is less than 3.5 or greater than 10.5 or more
When, a degree of dissolution will be occurred with the carrier that aluminium oxide is main carrier components, to will affect catalyst physical knot
Structure, and then influence the dispersity of active specy.
A preferred embodiment of the invention, the pH of the solution D are 4.5-5.5 or 8.5-9.5.It is excellent using this
PH value is selected to be more advantageous to the abundant of above-mentioned oxygen sulphur exchange reaction and rapidly carry out.
According to the present invention it is possible to adjust the pH value of solution D by various modes, there is no particular limitation to this by the present invention,
Such as the pH value of pH solution D is adjusted by the way that acid and/or alkali is added.The acid can be organic acid, be also possible to inorganic acid, this hair
It is bright that this, there is no particular limitation.
In accordance with the present invention it is preferred that the acid is in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid and citric acid
At least one, further preferably hydrochloric acid.Using preferred embodiment provided by the invention, the impurity element of introducing is in vulcanization type
Hydrogenation catalyst prepares late stage and can remove naturally, 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.
According to the present invention, the solvent of the solution D is preferably water.
A preferred embodiment of the invention, organic sulphur source are selected from sulphur shown in L- cysteine, formula (1)
For at least one of dithioesters shown in list monothioester shown in amide, formula (2) and formula (3),
In formula (1), R1For H, NH2-、CH3-、CH3CH2-、CH3NH- or (CH3)2N-, R2And R3Be 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.R2
And R3It can be identical or different.
The preparation method of a preferred embodiment of the invention, the hydrogenation catalyst includes:
(1) carrier is impregnated using the solution C containing vib metals compound, is dried to obtain solid A；
(2) solution D containing at least one organic sulphur source is contacted with solid A, then obtained solid product is carried out
It is dry；
Organic sulphur source be selected from list monothioester shown in L- cysteine, thioamides, formula (2) shown in formula (1) with
At least one of dithioesters shown in 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.
In accordance with the present invention it is preferred that organic sulphur source is thioamides shown in formula (1), it is still more preferably described
Organic sulphur source is thiocarbamide and/or thioacetamide, most preferably thioacetamide.
A preferred embodiment of the invention, concentration of organic sulphur source in solution D is 0.05-20mol/L, excellent
It is selected as 1-15mol/L, further preferably 4-10mol/L.
A preferred embodiment of the invention, this method further include pass-through mode 1) and/or mode 2) to adding hydrogen
Group VIII metallic element is introduced in catalyst；
Mode 1) it include: the addition group VIII metallic compound into solution C；
Mode 2) include: the substance that is dried to obtain using the solution E containing group VIII metallic compound to step (2) into
Row dipping.
Mode 1 of the present invention) in, when being added in group VIII metallic compound into solution C, if in solution C
Quantity of solvent be not enough to dissolve group VIII metallic compound, those skilled in the art can be as the case may be into solution C
It is added solvent (such as water).
Mode 2 of the present invention) in, the dipping can be saturation dipping, and (solvent of solution E is preferably solution E
Water) in group VIII metallic compound content group VIII metallic element according to needed for catalyst amount carry out
It determines, those skilled in the art can suitably be selected according to content in text.
A kind of specific embodiment according to the present invention, the mode 2) it further include being done to the resulting material of dipping
It is dry.Dry condition can be identical as drying condition described in step (1).
A preferred embodiment of the invention, group VIII metallic element are cobalt and/or nickel element.Described
Group VIII metal compound can be selected from nitrate, subcarbonate, chlorate, sulfate and the acetate of group VIII metal
At least one of.
A preferred embodiment of the invention, group VIII metallic compound, vib metals compound and load
The dosage of body makes, and in catalyst obtained, on the basis of the total amount of catalyst, the content of carrier is 54-85 weight %, with oxygen
Compound meter, the content of group VIII metallic element are 1-10 weight %, and the content of vib metals element is 8-45 weight %；
It is further preferred that the content of carrier is 68-84 weight % on the basis of the total amount of catalyst, and in terms of oxide, group VIII
The content of metallic element is 1.5-6 weight %, and the content of vib metals element is 10-30 weight %.
In the case of, according to the invention it is preferred to, the contact carries out in confined conditions.It operates in confined conditions, it is organic
The hydrogen sulfide that sulphur source hydrolyzes will not be discharged into air, neither will cause the pollution of air, and be more conducive to vulcanizing
Hydrogen is hydrolyzed to sulfidion, more efficient to utilize organic sulphur source.The contact can be in the autoclave that can bear thermal and hydric environment
Or carried out in closed reactor, the autoclave or closed reactor can bear 109The pressure of Pa.
The preparation method provided according to the present invention, it is preferable that the temperature of the contact is 60-120 DEG C, and the time is that 2-24 is small
When, it is further preferred that the temperature of contact is 70-100 DEG C, time 6-18h.It can be right using this kind of preferred contact conditions
The degree and speed of above-mentioned oxygen sulphur exchange have a direct impact, and then further improve the performance of catalyst, too low contact
Temperature will affect oxygen sulphur exchange degree and speed, increase the processing time, and excessively high temperature will affect carrier physical property again, into
And have an adverse effect to catalyst.The performance of catalyst can not only be improved using above-mentioned contact conditions, additionally it is possible to shorten system
It the standby time, improves efficiency.
There is no particular limitation to the mode for obtaining the solid product by the present invention, such as can be by being obtained by filtration.
In accordance with the present invention it is preferred that the condition of step (2) described drying include: inert atmosphere or reducing atmosphere (preferably
For inert atmosphere) under carry out, temperature be 100-250 DEG C, preferably 100-130 DEG C, the time be 1-12 hours, preferably 2-6 is small
When.
Preparation method according to the present invention, the inert atmosphere can be by one of nitrogen, argon gas and helium or a variety of
It provides, is preferably provided by nitrogen.
Preparation method according to the present invention, the reducing atmosphere can be by hydrogen and/or hydrogen sulfide and optionally inertia
Gas provides.
Inert gas can be contained in the reducing atmosphere, when in the reducing atmosphere contain inert gas when, hydrogen and/
Or the volume content of hydrogen sulfide is not less than 5%.
Catalyst provided by the invention only needs to carry out when going into operation simply living before use, do not need to carry out presulfurization
Vulcanization active metal component appropriate can be obtained in change processing, and obtains the II class A-B-S activity phase with greater catalytic performance.
Therefore, the present invention also provides the hydrogenation catalysts as made from above-mentioned preparation method.Above-mentioned plus hydrogen of the invention is urged
Agent can be adapted for various hydrogenation reactions, including but not limited to hydrofinishing, hydrotreating and be hydrocracked, especially suitable for
Hydrofining reaction.Therefore, the application the present invention also provides above-mentioned hydrogenation catalyst in hydrofinishing.The hydrofinishing
Including but not limited to hydrodesulfurization, hydrodenitrogeneration, hydrogenation aromatics-removing, removal of ccr by hydrotreating, hydrodemetallization and hydrogenation deoxidation.
The present invention also provides a kind of methods of hydrofinishing, this method comprises: by hydrogenation catalyst provided by the invention into
Row activation obtains activation rear catalyst, under Hydrofinishing conditions, in presence of hydrogen, by hydrogen refined material to be added and the work
Change rear catalyst 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 inert atmosphere or reducing atmosphere (preferably
For reducing atmosphere) under, 0.5-6h is activated at being 240-310 DEG C in temperature, activates 0.5- at being then 320-500 DEG C in temperature
6h.It was found by the inventors of the present invention that first being activated under low temperature (240-310 DEG C) in activation process, then in high temperature (320-500
DEG C) under activate, be more advantageous to improve activation rear catalyst sulphidity and addition agent modified degree, be more advantageous to improve catalyst plus
Hydrogen desulfurization performance.
The inert atmosphere or reducing atmosphere are as described above, and details are not described herein.
The sulphidity of a preferred embodiment of the invention, the activation rear catalyst is 65-90%, preferably
70-90%, more preferably 80-89%, and/or
Addition agent modified degree is 28-60%, preferably 35-52%, further preferably 43-50%.Activate rear catalyst
The test method of sulphidity and addition agent modified degree is as described above, and details are not described herein.
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 diesel oil model compound as an example, but this hair
It is bright to be not limited to this.
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 and comparative example, Components of Catalysts content is all made of X-ray fluorescence spectra analysis method RIPP
(petrochemical analysis method (RIPP experimental method), Yang Cuiding, Gu Kanying, Wu Wenhui are compiled 132-90, Science Press's nineteen ninety
The September first edition, the 371-379 pages) it measures.
The atomic ratio of sulphur and active metal component B pass through x-ray photoelectron spectroscopy analysis (XPS) measurement.
The sulphidity of host agent vib metals element is measured by x-ray photoelectron spectroscopy analysis (XPS) in catalyst,
In, 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.Addition agent modified degree is obtained by XPS data processing, specific processing method
It can be found in the chemical state [J] of active element in document X-ray photoelectron spectroscopy research Hydrobon catalyst, petroleum journal:
PETROLEUM PROCESSING, 2011,27 (4): 638-642.
Wherein, x-ray photoelectron spectroscopy analysis (XPS) is in ESCA Lab 250 model x-ray photoelectron spectroscopy (Britain
VG Products) on carry out, use radiation source for Al K α, resolution ratio 0.5eV, be inside designated as pollution carbon C1s combination energy
(Eb=285.0eV) condition obtains.
Embodiment 1
(1) solution C that 80mL contains 36.2g ammonium molybdate is prepared, then to 100g γ-Al2O3(diameter 1.5mm, specific surface
Product 250m2/ g, Kong Rongyue 0.8mL/g, similarly hereinafter) saturation dipping, solid A is obtained after 120 DEG C of dry 2h；
(2) aqueous solution for preparing 45mL thioacetamide containing 26.0g is dilute by the way that 2.4mol/L is added dropwise in whipping process
PH value is adjusted to 5 by nitric acid, obtains solution D；Solution D is transferred in the autoclave of the 100mL equipped with 60g solid A, then will
Autoclave is placed in rotary oven, is contacted 12 hours at 85 DEG C, solid product is obtained by filtration, under nitrogen protection, at 100 DEG C
Dry 3h obtains sulphided state catalyst S-1.XPS analysis shows that it contains a certain amount of MoS3Species, composition, sulphidity, S
It is listed in Table 1 below with the atomic ratio of Mo.
(3) 1g sulphided state catalyst S-1 is placed in hydrogenator, is 1h in hydrogen gas space velocity-1, hydrogen partial pressure is 4MPa's
Under the conditions of, it is handled 2 hours at 250 DEG C, the catalyst after 360 DEG C of processing are activated for 4 hours is then heated to, is calculated as A-
S-1.Sulphidity is listed in Table 1 below.
Comparative example 1
Solid A is obtained according to the method for 1 step of embodiment (1), vulcanization work is carried out to solid A using conventional cure method
Change, specifically: 1g solid A is seated in hydrogenator, use mass fraction for 3% CS2Cyclohexane solution is as sulphur
Agent, conditions of vulcanization include: H2Partial pressure is 4MPa, hydrogen gas space velocity 1.5h-1, temperature is 360 DEG C, time 4h, hydrogen to oil volume ratio
It is 500, the catalyst activated is denoted as A-C-1.The sulphidity of A-C-1 is listed in Table 1 below.
Comparative example 2
According to the method for embodiment 1, unlike, in terms of element sulphur, thioacetamide is replaced with to the sulphur of equimolar amounts
Change ammonium, obtains sulphided state catalyst C-2 and A-C-2, contain a certain amount of MoS in sulphided state catalyst C-23Species, composition,
The atomic ratio of sulphidity, S and Mo is listed in Table 1 below；The sulphidity of A-C-2 is listed in Table 1 below.
Embodiment 2
(1) solution C that 80mL contains 30g molybdenum trioxide, 8.45g phosphoric acid is prepared, then to 100g γ-Al2O3Saturation leaching
Stain obtains solid A after 120 DEG C of dry 2h；
(2) aqueous solution for preparing 60mL thioacetamide containing 36g, in whipping process, by the way that 2.4mol/L ammonium hydroxide is added dropwise
PH value is adjusted to 9, obtains solution D；Solution D is transferred in the autoclave of the 100mL equipped with 60g solid A, then by high pressure
Kettle is placed in rotary oven, contacts 18 hours at 70 DEG C, solid product is obtained by filtration, under nitrogen protection, dry at 100 DEG C
3h obtains sulphided state catalyst S-2.XPS analysis shows that it contains a certain amount of MoS3Species, composition, sulphidity, S and Mo
Atomic ratio be listed in Table 1 below.
(3) 1g sulphided state catalyst S-2 is placed in hydrogenator, is 1h in hydrogen gas space velocity-1, hydrogen partial pressure is 4MPa's
Under the conditions of, it is handled 2 hours at 250 DEG C, the catalyst after 360 DEG C of processing are activated for 4 hours is then heated to, is calculated as A-
S-2.Its sulphidity is listed in Table 1 below.
Comparative example 3
The solution C that 80mL contains 30g molybdenum trioxide, 8.45g phosphoric acid is prepared, then to 100g γ-Al2O3Saturation dipping, warp
Obtain solid A after 120 DEG C of dry 2h, vulcanization activation carried out to solid A using conventional cure method, conditions of vulcanization with comparative example 1,
The catalyst activated, is denoted as A-C-3.The sulphidity of A-C-3 is listed in Table 1 below.
Embodiment 3
(1) solution C that 80mL contains 43.0g ammonium metatungstate is prepared, then to 100g γ-Al2O3Saturation dipping, through 120 DEG C
Solid A is obtained after dry 2h；
(2) aqueous solution for preparing 80mL thioacetamide containing 40g, in whipping process, by the hydrogen that 2.4mol/L is added dropwise
PH value is adjusted to 9.5 by sodium oxide molybdena, obtains solution D；Solution D is transferred in the autoclave of the 100mL equipped with 60g solid A, so
Autoclave is placed in rotary oven afterwards, is contacted 10 hours at 90 DEG C, solid product is obtained by filtration, under nitrogen protection, in 100
Dry 3h obtains sulphided state catalyst S-3 at DEG C.XPS analysis shows that it contains a certain amount of WS3Species, composition, vulcanization
The atomic ratio of degree, S and W is listed in Table 1 below.
(3) 1g sulphided state catalyst S-3 is placed in hydrogenator, is 1h in hydrogen gas space velocity-1, hydrogen partial pressure is 4MPa's
Under the conditions of, it is handled 2 hours at 250 DEG C, the catalyst after 360 DEG C of processing are activated for 4 hours is then heated to, is calculated as A-
S-3.Its sulphidity is listed in Table 1 below.
Comparative example 4
Solid A is obtained according to the method for 3 step of embodiment (1), vulcanization work is carried out to solid A using conventional cure method
Change, for conditions of vulcanization with comparative example 1, the catalyst activated is denoted as A-C-4.The sulphidity of A-C-4 is listed in Table 1 below.
Embodiment 4
(1) with embodiment 1；
(2) aqueous solution for preparing 45mL thioacetamide containing 30g, in whipping process, by the way that 2.4mol/L hydrochloric acid is added dropwise
PH value is adjusted to 4.5, obtains solution D；Solution D is transferred in the autoclave of the 100mL equipped with 60g solid A, it then will be high
Pressure kettle is placed in rotary oven, contacts 6 hours at 100 DEG C, solid product is obtained by filtration, and under nitrogen protection, is done at 100 DEG C
Dry 3h obtains sulphided state catalyst S-4.XPS analysis shows that it contains a certain amount of MoS3Species, composition, sulphidity, S with
The atomic ratio of Mo is listed in Table 1 below.
(3) 1g sulphided state catalyst S-4 is placed in hydrogenator, is 1h in hydrogen gas space velocity-1, hydrogen partial pressure is 4MPa's
Under the conditions of, it is handled 2 hours at 250 DEG C, the catalyst after 360 DEG C of processing are activated for 4 hours is then heated to, is calculated as A-
S-4.Its sulphidity is listed in table 1.
Embodiment 5
According to the method for embodiment 1, unlike, step (1) prepares 80mL and contains 43.0g ammonium metatungstate and 6.45g phosphorus
The solution C of acid.Sulphided state catalyst S-5 and A-S-5 are obtained, contains a certain amount of MoS in sulphided state catalyst S-53Species,
Composition, sulphidity, S and Mo atomic ratio be listed in Table 1 below；The sulphidity of A-S-5 is listed in Table 1 below.
Embodiment 6
According to the method for embodiment 1, unlike, in step (2), pH value is adjusted to by the way that 2.4mol/L hydrochloric acid is added dropwise
3.5.Sulphided state catalyst S-6 and A-S-6 are obtained, contains a certain amount of MoS in sulphided state catalyst S-63Species, composition,
The atomic ratio of sulphidity, S and Mo is listed in Table 1 below；The sulphidity of A-S-6 is listed in Table 1 below.
Embodiment 7
According to the method for embodiment 1, unlike, in step (1), pH value is adjusted to by the way that 2.4mol/L ammonium hydroxide is added dropwise
10.5.Sulphided state catalyst S-7 and A-S-7 are obtained, contains a certain amount of MoS in sulphided state catalyst S-73Species, composition,
The atomic ratio of sulphidity, S and Mo is listed in Table 1 below；The sulphidity of A-S-7 is listed in Table 1 below.
Embodiment 8
According to the method for embodiment 1, unlike, in step (2), solution D is transferred to the 100mL equipped with 60g solid A
Autoclave in, then autoclave is placed in rotary oven, 60 DEG C contact 12 hours.Obtain sulphided state catalyst S-8 and
Contain a certain amount of MoS in A-S-8, sulphided state catalyst S-83Species, composition, sulphidity, S and Mo atomic ratio be listed in table
In 1；The sulphidity of A-S-8 is listed in Table 1 below.
Embodiment 9
According to the method for embodiment 1, unlike, in step (2), solution D is transferred to the 100mL equipped with 60g solid A
Autoclave in, then autoclave is placed in rotary oven, 140 DEG C contact 12 hours.Obtain sulphided state catalyst S-9 and
Contain a certain amount of MoS in A-S-9, sulphided state catalyst S-93Species, composition, sulphidity, S and Mo atomic ratio be listed in table
In 1；The sulphidity of A-S-9 is listed in Table 1 below.
Embodiment 10
According to the method for embodiment 1, unlike, in step (2), pH value is adjusted to by the way that 2.4mol/L hydrochloric acid is added dropwise
2.Sulphided state catalyst S-10 and A-S-10 are obtained, contains a certain amount of MoS in sulphided state catalyst S-103Species, composition,
The atomic ratio of sulphidity, S and Mo is listed in Table 1 below；The sulphidity of A-S-10 is listed in Table 1 below.
Embodiment 11
According to the method for embodiment 1, unlike, in step (2), pH value is adjusted to by the way that 2.4mol/L ammonium hydroxide is added dropwise
11.5.Sulphided state catalyst S-11 and A-S-11 are obtained, contains a certain amount of MoS in sulphided state catalyst S-113Species, group
It is listed in Table 1 below at, the atomic ratio of sulphidity, S and Mo；The sulphidity of A-S-11 is listed in Table 1 below.
Embodiment 12
According to the method for embodiment 1,80mL, which is prepared, unlike, in step (1) contains 36.2g ammonium molybdate, 26g nickel nitrate
Solution C.Sulphided state catalyst S-12 and A-S-12 are obtained, contains a certain amount of MoS in sulphided state catalyst S-123Species,
Its composition, sulphidity, S and Mo atomic ratio be listed in Table 1 below；The sulphidity of A-S-12 and addition agent modified degree are listed in Table 1 below.
Embodiment 13
According to the method for embodiment 1, unlike, this method further includes preparing the solution E of the nickel nitrate containing 26g of 48mL,
Saturation dipping is carried out using solution E sulphided state catalyst S-1 resulting to step (2), obtains sulphided state after 120 DEG C of dry 2h
Catalyst S-13；Sulphided state catalyst S-13 is activated according to the method for 1 step of embodiment (3), obtains A-S-13, is vulcanized
Contain a certain amount of MoS in state catalyst S-133Species, composition, sulphidity, S and Mo atomic ratio be listed in Table 1 below；A-S-
13 sulphidity and addition agent modified degree are listed in Table 1 below.
Table 1
Test example 1
The catalyst that above-described embodiment and comparative example are provided carries out hydrodesulfurization activity evaluation.
The evaluation of hydrodesulfurization activity: raw material be respectively dibenzothiophenes (DBT) mass content 1% n-heptane solution and
The n-heptane solution of 4,6- dimethyl Dibenzothiophene (4,6-DMDBT) mass content 0.45%；Reaction condition are as follows: 4.0MPa,
345 DEG C, hydrogen to oil volume ratio 400, liquid hourly space velocity (LHSV) 2.0h-1.After stable reaction 3h, sampled every 4h, with gas Chromatographic Determination plus
Sulfur content in the raw material of hydrogen desulphurization reaction and the product of acquisition, every sample measurement three times, take its average value.By DBT and 4,6-
DMDBT hydrodesulfurization reaction is as first order reaction processing, and catalyst hydrodesulfurization active is with relative to reference agent D (comparative example 1)
Hydrodesulfurization activity indicate, by formula (1) calculating catalyst opposite hydrodesulfurization activity:
In formula, k (S) represents the hydrodesulfurization activity of catalyst, k (DS) represent the hydrodesulfurization of reference agent D (comparative example 1)
Activity.
In formula, SSpSulphur mass percentage in reaction product to use catalyst；SSfTo use the reaction of catalyst former
Sulphur mass percentage in material；SDpSulphur mass percentage in reaction product to use reference agent D；SDfTo use reference agent D
Reaction raw materials in sulphur mass percentage, the hds evaluation result such as table of catalyst obtained by each embodiment and comparative example
Shown in 2.
Table 2
It can be illustrated by the result of table 1, table 2, compared with the hydrogenation catalyst of conventional method preparation, with the method provided by the present invention
The amount of activated metal component B of the sulphided state hydrogenation catalyst being prepared exists in the form of trisulfide, remainder activity gold
Belonging to component B to exist in the form of trioxide, for the atomic ratio of sulphur and active metal component B between 2.1-2.9, sulphidity is moderate,
Suitable with the binding force of carrier, after being simply activated, catalyst vulcanization degree is high, when containing active metal component A, auxiliary agent
Degree of modification is high, substantially increases the utilization rate of active metal, it is even more important that although two class catalyst composition is similar,
Catalyst provided by the invention has considerably better hydrodesulfurization activity.The above results sufficiently show provided by the present invention
Prepare the superiority for having vulcanization method incomparable.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (15)
1. a kind of hydrogenation catalyst, which includes the active metal component B of carrier and load on this carrier, activity gold
Belong to component B and be selected from least one of vib metals element, which is characterized in that amount of activated metal component B is with trisulfide
Form exists, and remainder active metal component B exists in the form of trioxide, measured as x-ray photoelectron spectroscopy described in
In catalyst, the atomic ratio of sulphur and active metal component B are 2.1-2.9, and the sulphidity of catalyst is 40-80%.
2. hydrogenation catalyst according to claim 1, wherein the atomic ratio of sulphur and active metal component B are 2.5-2.8；
Preferably, the active metal component B is molybdenum and/or wolfram element；
Preferably, the carrier is selected from gama-alumina, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-oxygen
Change magnesium, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, oxygen
Change titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia and
One of silica-alumina, zirconia is a variety of.
3. hydrogenation catalyst according to claim 1, wherein the sulphidity of the hydrogenation catalyst is 60-85%, preferably
65-72%；And/or
The hydrogenation catalyst is after being activated, sulphidity 65-90%, preferably 70-90%, more preferably 80-89%；
It is 1h that the condition of the activation processing, which includes: in hydrogen gas space velocity,-1, under conditions of hydrogen partial pressure is 4MPa, handled 2 hours at 250 DEG C,
360 DEG C are then heated to handle 4 hours.
4. hydrogenation catalyst described in any one of -3 according to claim 1, wherein on the basis of the total amount of catalyst, carry
The content of body is 60-90 weight %, preferably 70-85 weight %, and in terms of oxide, the content of active metal component B is 10-40
Weight %, preferably 15-30 weight %.
5. hydrogenation catalyst described in any one of -3 according to claim 1, wherein the catalyst further includes being supported on carrier
On active metal component A, active metal component A is selected from least one of group VIII metallic element；And/or
The hydrogenation catalyst through activation processing after, it is addition agent modified degree be 28-60%, preferably 35-52%, further preferably
43-50%, the addition agent modified degree refer to the active metal component A measured by X-ray electron spectrum with II class activity phase A-
The ratio of B-S form existing amount and active metal component A total amount；The condition of the activation processing includes: to be in hydrogen gas space velocity
1h-1, under conditions of hydrogen partial pressure is 4MPa, handled 2 hours at 250 DEG C, then heat to 360 DEG C and handle 4 hours；
Preferably, the active metal component A is cobalt and/or nickel element.
6. hydrogenation catalyst according to claim 5, wherein on the basis of the total amount of catalyst, the content of carrier is 54-
85 weight %, in terms of oxide, the content of active metal component A is 1-10 weight %, and the content of active metal component B is 8-45
Weight %；
Preferably, on the basis of the total amount of catalyst, the content of carrier is 68-84 weight %, in terms of oxide, active metal group
The content for dividing A is 1.5-6 weight %, and the content of active metal component B is 10-30 weight %.
7. a kind of preparation method of hydrogenation catalyst, wherein this method comprises:
(1) carrier is impregnated using the solution C containing vib metals compound, is dried to obtain solid A；
(2) solution D containing at least one organic sulphur source is contacted with solid A, then obtained solid product is dried；
Organic sulphur source is the sulphur-containing substance that can be hydrolyzed in solution D and/or under contact conditions, and the temperature of the contact is
20-150 DEG C, the time is not less than 0.5 hour.
8. preparation method according to claim 7, wherein the pH of the solution D is 3.5-6.5 or 7.5-10.5；
Preferably, the pH of the solution D is 4.5-5.5 or 8.5-9.5.
9. preparation method according to claim 7 or 8, wherein organic sulphur source is selected from L- cysteine, formula (1) institute
At least one of dithioesters shown in list monothioester shown in the thioamides that shows, formula (2) and formula (3),
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)；
Preferably, the molar ratio of organic sulphur source and the vib metals compound is 2-6:1, preferably 3-6:1,
In, organic sulphur source is in terms of element sulphur, and vib metals compound is in terms of vib metals element；
Preferably, concentration of organic sulphur source in solution D be 0.05-20mol/L, preferably 1-15mol/L, further preferably
4-10mol/L。
10. the preparation method according to any one of claim 7-9, wherein vib metals element be molybdenum and/or
Wolfram element, the vib metals compound are selected from molybdenum trioxide, tungstic acid, ammonium molybdate, sodium molybdate, sodium tungstate, wolframic acid
At least one of ammonium, metamolybdic acid ammonium, ammonium metatungstate, ammonium phosphomolybdate and ammonium phosphotungstate；
The carrier is selected from gama-alumina, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-magnesias, oxygen
SiClx-zirconium oxide, silica thoria, silica-berylias, silica-titania, silica-zirconia, titanium oxide-oxygen
Change zirconium, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia and silica-
One of aluminium oxide-zirconium oxide is a variety of；
Preferably, the dosage of vib metals compound and carrier makes, and in catalyst obtained, is with the total amount of catalyst
The content of benchmark, carrier is 60-90 weight %, and preferably 70-85 weight %, in terms of oxide, vib metals element contains
Amount is 10-40 weight %, preferably 15-30 weight %.
11. the preparation method according to any one of claim 7-9, wherein
This method further includes pass-through mode 1) and/or mode 2) group VIII metallic element is introduced into hydrogenation catalyst；
Mode 1) it include: the addition group VIII metallic compound into solution C；
Mode 2) it include: to be soaked using the substance that the solution E containing group VIII metallic compound is dried to obtain step (2)
Stain；
Preferably, group VIII metallic element is cobalt and/or nickel element, and the group VIII metallic compound is selected from group VIII
At least one of nitrate, subcarbonate, chlorate, sulfate and acetate of metal；
Preferably, the dosage of group VIII metallic compound, vib metals compound and carrier makes, catalyst obtained
In, on the basis of the total amount of catalyst, the content of carrier is 54-85 weight %, in terms of oxide, group VIII metallic element
Content is 1-10 weight %, and the content of vib metals element is 8-45 weight %；It is further preferred that with the total of catalyst
On the basis of amount, the content of carrier is 68-84 weight %, and in terms of oxide, the content of group VIII metallic element is 1.5-6 weight
% is measured, the content of vib metals element is 10-30 weight %.
12. the preparation method according to any one of claim 7-11, wherein the temperature of the contact is 60-120
DEG C, the time is 2-24 hours, it is preferable that the temperature of contact is 70-100 DEG C, time 6-18h；
Preferably, the contact carries out in confined conditions；
Preferably, the condition of step (2) described drying includes: to carry out under inert atmosphere or reducing atmosphere, temperature 100-250
DEG C, preferably 100-130 DEG C, the time is 1-12 hours, preferably 2-6 hours.
13. hydrogenation catalyst made from the preparation method as described in any one of claim 7-12.
14. application of the hydrogenation catalyst in hydrofinishing described in any one of claim 1-6 and 13.
15. a kind of method of hydrofinishing, this method comprises: by adding hydrogen to urge described in any one of claim 1-6 and 13
Agent is activated to obtain activation rear catalyst, under Hydrofinishing conditions, in presence of hydrogen, by hydrogen refined material to be added with
The activation rear catalyst is contacted；
Preferably, the condition of the activation includes: and activates at being 240-500 DEG C in temperature under inert atmosphere or reducing atmosphere
1-12h；
It is further preferred that the condition of the activation includes: under inert atmosphere or reducing atmosphere, it is 240-310 DEG C in temperature
Lower activation 0.5-6h activates 0.5-6h at being then 320-500 DEG C in temperature.
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