Hydrogenation catalyst preparation method and by this method preparation hydrogenation catalyst and application
阅读说明：本技术 加氢催化剂制备方法和由该方法制备的加氢催化剂及应用 (Hydrogenation catalyst preparation method and by this method preparation hydrogenation catalyst and application ) 是由 韩伟 龙湘云 杨清河 邓中活 于 2018-05-21 设计创作，主要内容包括：本发明涉及加氢精制领域,公开了一种加氢催化剂制备方法和由该方法制备的催化剂及应用,所述制备方法包括如下步骤：(1)将四硫代钼酸盐和第VIII族金属盐引入到载体上,得到复合材料A；(2)在惰性气氛或还原气氛下对复合材料A进行热处理,所述热处理使得复合材料A中Mo以三硫化物形式存在,第VIII族金属元素以盐的形式存在。本发明提供的制备方法省去了硫化过程,所制备的催化剂活性组分充分硫化,催化剂加氢性能有明显提升。(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.)
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.
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.