CN101590437B - Ex-situ presulfurizing method of hydrogenation catalyst - Google Patents
Ex-situ presulfurizing method of hydrogenation catalyst Download PDFInfo
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Abstract
The invention provides an ex-situ presulfurizing method of a hydrogenation catalyst, adopting thioacetamide (CH3CSNH2) as a vulcanizing agent to pretreat the hydrogenation catalyst in oxidation state. The hydrogenation catalyst is mainly used for treating hydrocarbon materials. The vulcanizing agent can be used separately, or can be used in combination with other sulfides. The vulcanizing agent prepared by the method in the invention has the advantages that the cost is low, the method can solve the existing problem of high production cost of the organic vulcanizing agent; furthermore, the technique has the advantages of easy preparation method and equipment, little pollution and easy operation and the like; on the basis of the above advantages, the presulfurizing catalyst prepared by the presulfurizing method in the invention can reach or surpass the effect of in-situ presulfurizing method featuring complex operation and high cost, thus having wide application prospect in the ex-situ presulfurizing technique of hydrogenation catalysts.
Description
Technical field
The present invention relates to a kind of outer method for pre-sulphuration of device of the hydrogenation catalyst mainly for the treatment of hydro carbons.
Background technology
Along with the minimizing of world oil reserves, crude oil heaviness trend is day by day obvious, and sulphur, nitrogen, metal equal size increase in the crude oil.In order to take full advantage of limited resources, environmental contamination reduction, hydrogen addition technology becomes very important processing link in the petroleum refining industry, wherein, used hydrogenation catalyst contains group vib hydrogenation active metals molybdenum and/or tungsten usually, with group VIII hydrogenation active metals nickel and/or cobalt, before use, these reactive metals all are present in the catalyst with the form of oxidation state, in the hydrogenation transfer process, though owing to contain sulfide in the feedstock oil, change into sulphided state by reaction, but because under reaction condition, sulfur content is excessively low in the feedstock oil, sulfuration not exclusively causes a part of metallic reducing, makes catalyst activity not reach normal level, therefore, in actual use, before carrying out hydroconversion reactions, need hydrogenation catalyst is carried out presulfurization.
The method of hydrogenation presulfurization is divided into two large classes, i.e. the outer presulfurization method of presulfurization and device in the device.Presulfurization is about to catalyst and packs into and carry out presulfurization behind the hydrogenation plant again in the device.The shortcoming of the method is that cost is high, cure time is long, uses inflammable and poisonous sulfide, to environment, and also also quite strict to the requirement for the treatment of apparatus.For this reason, developed the outer presulfurization method technique of device, first hydrogenation catalyst is combined with vulcanizing agent (its process is carried out outside hydrogenation reactor), only need pass into hydrogen when going into operation or pass into the oil product of hydrogen, heat up subsequently and can finish sulfuration, have simple, efficient, pollution-free and advantage cheaply.
Chinese patent literature CN1262305 discloses a kind of method for pre-sulphuration of hydrogenation catalyst, comprises that (1) with the method for distillation and/or fusing, contacts described catalyst with elementary sulfur, and the temperature of contact enters in the hole of catalyst described elementary sulfur basically; (2) a kind of component, elementary sulfur and auxiliary agent that contains alkene mixed, more than 0.5 hour, wherein, described auxiliary agent is selected from one or more in the vulcanization of rubber organic additive commonly used at the 100-220 ℃ of described mixture of heating; The catalyst that the product impregnation steps (1) of the Containing Sulfur alkene that (3) step (2) is obtained obtains, and under inert atmosphere in 100-300 ℃ of heatable catalyst more than 1 hour.The shortcoming that this technique exists is that (1) uses elementary sulfur as vulcanizing agent, and is large to the harmfulness of human body; (2) technological process and operating procedure are complicated, need with elementary sulfur catalyst to be processed first, with the organic matter that contains sulphur this catalyst are flooded again, and the catalyst behind the dipping also need be heat-treated (＞100 ℃) etc.
US4719195 discloses a kind of method for pre-sulphuration of hydrogenation catalyst, vulcanizing agent is added in the catalyst, exist at no hydrogen, temperature is lower than in 275 ℃ the situation, and reactive metal oxides is vulcanized, and catalyst activated being higher than under 275 ℃ the temperature again.Wherein, used vulcanizing agent is that a kind of general formula is the polysulfide of R-S (n)-R ' chemical formula, n is 3～20 in the formula, R and R ' can be identical or different, each group contains 1～150 carbon atom, and each group is comprised of saturated or undersaturated straight or branched type alkyl, aryl, alkaryl and aralkyl.R ' can also be hydrogen atom.The shortcoming of this technique is that the consumption of polysulfide is more, and it is not high to hold sulfur content.
US5139990 then adopts the liquid medium presulfurization hydrogenation catalyst that contains organic sulfur compound, and used organic sulfur compound is: thiocarbamide, thiocyanic acid sodium, dimethyl sulfoxide (DMSO), 3,4-dithia adipate, 2,2-dithioglycol.The shortcoming of the method is to make vulcanizing agent with organic sulfur compound, and used vulcanizing agent is more expensive than elemental sulfur, adopts a large amount of expensive organic sulfur compounds to improve the presulfurization cost as vulcanizing agent, is unfavorable for industrial practical application.
CN1557556A discloses a kind of hydrogenation catalyst presulfurizing method, and it adopts elementary sulfur is dissolved in (NH
4)
2Method preparation in the S solution.In fact, the inorganic polymeric form sulfide of this method preparation is a kind of mixture, and composition comprises elementary sulfur, (NH
4)
2S and (NH
4)
2S
X(X is generally 3～9 greater than 2).In catalyst activation process, these materials are different from the temperature range of hydrogen effect, therefore can reduce concentrated heat release, prevent that beds from significantly heating up.But select it to have following shortcoming as vulcanizing agent: (1) needs at least double-steeping just can reach and necessarily holds sulfur content, and last drying must be carried out in inert atmosphere; Emit the harmful substances such as hydrogen sulfide when (2) dry.
Summary of the invention
For this reason, technical problem to be solved by this invention is to propose that a kind of processing step is simple, cost of manufacture is low, to hold sulfur content high and pollute the outer method for pre-sulphuration of device of little hydrogenation catalyst.
For solving the problems of the technologies described above, the outer method for pre-sulphuration of the device of a kind of hydrogenation catalyst of the present invention may further comprise the steps:
(a) the solution impregnation hydrogenation catalyst of usefulness thioacetamide and auxiliary agent thereof;
(b) the catalyst inert gas purge that above-mentioned steps is obtained.
Said method can also comprise step (c), and the catalyst that is about to obtain in the step (b) is packed in the reactor, heats up in hydrogen atmosphere and finishes sulfidation.
In described step (a), described solution is the aqueous solution or alcoholic solution.
In described step (a), described auxiliary agent is selected from mercaptan, thiocarbamide, thiophene and derivatives or polysulfide.
Described auxiliary agent is thiophene and derivatives.
Described inert gas is nitrogen.
The mol ratio of tenor is 0.5: 1 to 3: 1 in described thioacetamide and the described hydrogenation catalyst.
The mol ratio of tenor is 0.5: 1 to 2: 1 in described thioacetamide and the described hydrogenation catalyst.
The amount of described auxiliary agent is 0～50w% of described thioacetamide addition.
The content of described auxiliary agent is 10～30w% of described thioacetamide addition.
Described alcoholic solvent is normal propyl alcohol.
The temperature of the described hydrogenation catalyst of solution impregnation of described thioacetamide and auxiliary agent thereof is room temperature to 60 ℃, and dip time is 5～30 hours.
Described step (b) is under room temperature to 160 ℃, with nitrogen blowing 1～10 hour.
In described step (c), be under 200 ℃～500 ℃ the hydrogen atmosphere, to process 1～10 hour in temperature.
Described hydrogenation catalyst be more than one metal by group vib metal molybdenum and/or tungsten and VIII family metallic cobalt and/or nickel as active component, and load on aluminium oxide and modifier thereof, molecular sieve, the activity carbon carrier with the form of oxide.
Described thioacetamide is as the purposes of the vulcanizing agent of hydrogenation catalyst presulfurizing.
Technique scheme of the present invention compared with prior art has the following advantages, (1) the present invention adopts thioacetamide to carry out the presulfurization of hydrogenation catalyst as vulcanizing agent, this sulfide has higher solubility and contains high activity lower valency sulphur in water and ethanol, can at room temperature finish the O-S exchange with oxide, the S-H reaction occurs in the hydrogen atmosphere, finish degree of depth sulfuration under the high temperature, therefore described hydrogenation catalyst product sulfur content is higher; In addition, described thioacetamide can form suitable metal sulfide micromeritics lamella with metal oxide under the acidic catalyst carrier function, suppresses activity and assembles mutually, improves activity, stability and the life-span of catalyst; (2) the present invention adopts mercaptan, thiophene and derivatives, polysulfide as auxiliary agent, and the interpolation of these auxiliary agents has improved holds sulfur content; (3) the outer method for pre-sulphuration of the device of hydrogenation catalyst of the present invention, the equipment and process process is simple, and used vulcanizing agent thioacetamide is cheap for chemical products commonly used, and therefore whole method for pre-sulphuration is with low cost, is suitable for very much promoting; (4) the outer method for pre-sulphuration of the device of hydrogenation catalyst of the present invention, also have and pollute little advantage, its former because 1. be added on vulcanizing agent on the hydrogenation catalyst be thioacetamide and described hydrogenation catalyst interaction well, vulcanizing agent is difficult for running off when going into operation, the amount of required vulcanizing agent is less, therefore pollutes little; 2. the alcoholic solution of thioacetamide has preferably diffusivity at hydrogenation catalyst, can make hydrogenation catalyst adsorb more thioacetamide, rather than be deposited in catalyst surface, therefore pollutes little; 3. flooding the used solvent of described hydrogenation catalyst is ethanol or water, and they obtain easily and remove and be own pollution-free.
The specific embodiment
The present invention adopts thioacetamide as the vulcanizing agent of hydrogenation catalyst presulfurizing, its principle is, thioacetamide has higher solubility and contains high activity lower valency sulphur in water and ethanol, can at room temperature finish the O-S exchange with oxide, the S-H reaction occurs in the hydrogen atmosphere, at high temperature finishes degree of depth sulfuration.
In addition, described thioacetamide can form suitable metal sulfide micromeritics lamella with metal oxide under the acidic catalyst carrier function, suppresses activity and assembles mutually, improves activity, stability and the life-span of catalyst.
The used hydrogenation catalyst of following examples is a kind of catalyst (hereinafter to be referred as commercial catalysts) commonly used in the Chemical Manufacture, i.e. load molybdenum oxide and cobalt oxide on aluminium oxide, wherein, MoO
3Percentage by weight is that 15.1%, CoO percentage by weight is 4.3%, and specific surface is 254m
2/ g, pore volume are 0.55ml/g; Diameter is 2.0mm, and water absorption rate is 0.5ml/g.
Estimating the used raw material of activity of hydrocatalyst in following examples is cracked diesel oil, it is characterized by: density (d
4 20) be 0.893g/cm3, sulfur content is 6154 μ g/g, and nitrogen content is 1035 μ g/g, and aniline point is 49.0 ℃, and Cetane number is 35.8, boiling range is 171～362 ℃.
Embodiment 1:
(1) takes by weighing the 6.1g thioacetamide and at room temperature join in the 90ml deionized water, stir, dissolving.
(2) take by weighing commercial catalysts 100g and add in the described solution of step (1) and flood, at room temperature leave standstill 30 hours after, dry, then put into tube furnace, under 120 ℃, passed into nitrogen treatment 8 hours, obtain catalyst A.
(3) carry out the diesel oil hydrogenation activity rating at small-sized continously hydrogen adding reaction unit, reactor is 25mm * 800mm stainless steel tube, and the amount of fill of catalyst is 100ml.
The 100ml catalyst A is packed in the hydrogenation reactor, pass into hydrogen, Adjustment System pressure is 6.0MPa, amounts of hydrogen is 800ml/min, heating rate with 35 ℃/h is warming up to 120 ℃ with reactor, constant temperature made the catalyst dehydration in 2 hours, then the heating rate with 35 ℃/h is warming up to 200 ℃ with reactor, constant temperature activated catalyst in 10 hours fully, begin again to pump into above-mentioned cracked diesel oil, pump discharge is 100ml/h, then with the heating rate of 40 ℃/h the temperature of reactor is risen to 350 ℃, keeps this temperature sample analysis after 48 hours.Evaluation result sees Table 1.
Embodiment 2:
(1) takes by weighing 36.5g thioacetamide and 3.7g ethyl mercaptan and at room temperature join in the 90ml normal propyl alcohol, stir, dissolving.
(2) take by weighing commercial catalysts 100g and add in the described solution of step (1) and flood, at room temperature leave standstill 30 hours after, dry, then put into tube furnace, at room temperature passed into nitrogen treatment 10 hours, obtain catalyst B.
(3) carry out the diesel oil hydrogenation activity rating at small-sized continously hydrogen adding reaction unit, reactor is 25mm * 800mm stainless steel tube, and the amount of fill of catalyst is 100ml.
The 100ml catalyst B is packed in the hydrogenation reactor, pass into hydrogen, Adjustment System pressure is 6.0MPa, amounts of hydrogen is 800ml/min, heating rate with 35 ℃/h is warming up to 120 ℃ with reactor, constant temperature made the catalyst dehydration in 2 hours, and then the heating rate with 35 ℃/h is warming up to 300 ℃ with reactor, and constant temperature activated catalyst in 10 hours fully.After finishing the temperature of reactor is down to 200 ℃, begins to pump into above-mentioned cracked diesel oil, pump discharge is 100ml/h, then with the heating rate of 40 ℃/h the temperature of reactor is risen to 350 ℃, keeps this temperature sample analysis after 48 hours.Evaluation result sees Table 1.
Embodiment 3:
(1) takes by weighing 24.3g thioacetamide and 7.3g thiophene and under 60 ℃, join in the 90ml normal propyl alcohol, stir, dissolving.
(2) take by weighing commercial catalysts 100g and add in the described solution of step (1) and flood, under temperature 60 C, leave standstill 5 hours after, dry, then put into tube furnace, under 100 ℃, passed into nitrogen treatment 8 hours, obtain catalyst C.
(3) carry out the diesel oil hydrogenation activity rating at small-sized continously hydrogen adding reaction unit, reactor is 25mm * 800mm stainless steel tube, and the amount of fill of catalyst is 100ml.
100ml catalyst C is packed in the hydrogenation reactor, pass into hydrogen, Adjustment System pressure is 6.0MPa, amounts of hydrogen is 800ml/min, heating rate with 35 ℃/h is warming up to 120 ℃ with reactor, constant temperature made the catalyst dehydration in 2 hours, and then the heating rate with 35 ℃/h is warming up to 500 ℃ with reactor, and constant temperature activated catalyst in 1 hour fully.After finishing the temperature of reactor is down to 200 ℃, begins to pump into above-mentioned cracked diesel oil, pump discharge is 100ml/h, then with the heating rate of 40 ℃/h the temperature of reactor is risen to 350 ℃, keeps this temperature sample analysis after 48 hours.Evaluation result sees Table 1.
Embodiment 4:
(1) takes by weighing 13g thioacetamide and 3.3g tetramethylthiuram disulfide and under 40 ℃, join in the 90ml normal propyl alcohol, stir, dissolving.
(2) taking by weighing commercial catalysts 100g adds in the described solution of step (1) and floods; After under 40 ℃ of temperature, leaving standstill 10 hours, dry, then put into tube furnace, under 160 ℃, passed into nitrogen treatment 1 hour, obtain catalyst D.
(3) carry out the diesel oil hydrogenation activity rating at small-sized continously hydrogen adding reaction unit, reactor is 25mm * 800mm stainless steel tube, and the amount of fill of catalyst is 100ml.
100ml catalyst D is packed in the hydrogenation reactor, pass into hydrogen, Adjustment System pressure is 6.0MPa, amounts of hydrogen is 800ml/min, heating rate with 35 ℃/h is warming up to 120 ℃ with reactor, constant temperature made the catalyst dehydration in 2 hours, and then the heating rate with 35 ℃/h is warming up to 300 ℃ with reactor, and constant temperature activated catalyst in 4 hours fully.After finishing the temperature of reactor is down to 200 ℃, begins to pump into above-mentioned cracked diesel oil, pump discharge is 100ml/h, then with the heating rate of 40 ℃/h the temperature of reactor is risen to 350 ℃, keeps this temperature sample analysis after 48 hours.Evaluation result sees Table 1.
Embodiment 5:
Prepare take ZSM-5 molecular sieve composite Ti O as carrier, with MoO according to patent CN1128858C
3, NiO is the hydrogenation catalyst of active component.Preparation process is as follows: industrial hydrous titanium oxide 100g, SB powder 60g, ZSM-5 molecular sieve 50g through the zinc nitrate modification, wherein zinc nitrate accounts for 5% of ZSM-5 molecular sieve after the modification, after the mixing, adds 7g sesbania powder, the 21g polyethylene glycol, the 4g citric acid, 25ml nitric acid (65%) and appropriate amount of deionized water, kneading extrusion (φ 1.6mm).At 110 ℃ of lower dry 4h, again at 550 ℃ of lower roasting 4h, obtain carrier.With stablizing maceration extract (ammonium molybdate 50g/ deionized water 100ml, nickel nitrate 36.6g/ deionized water 100ml) the above-mentioned carrier of incipient impregnation.Leave standstill 10h under the room temperature, at 110 ℃ of lower dry 4h, at 500 ℃ of roasting 4h, the catalyst that obtains consists of: MoO
3Percentage by weight is that 12.1%, NiO percentage by weight is 4.8%.
Below be the pre-vulcanization process of the hydrogenation catalyst by said method preparation and to its activity rating:
(1) takes by weighing 16g thioacetamide and 5.2g thiocarbamide and under 40 ℃, join in the 90ml normal propyl alcohol, stir, dissolving.
(2) taking by weighing the described catalyst 100g of step (1) adds in the described solution of step (1) and floods; After under 40 ℃ of temperature, leaving standstill 15 hours, dry, then put into tube furnace, under 80 ℃, passed into nitrogen treatment 4 hours, obtain catalyst E.
(3) carry out the diesel oil hydrogenation activity rating at small-sized continously hydrogen adding reaction unit, reactor is 25mm * 800mm stainless steel tube, and the amount of fill of catalyst is 100ml.
100ml catalyst E is packed in the hydrogenation reactor, pass into hydrogen, Adjustment System pressure is 6.0MPa, amounts of hydrogen is 800ml/min, heating rate with 35 ℃/h is warming up to 120 ℃ with reactor, constant temperature made the catalyst dehydration in 2 hours, and then the heating rate with 35 ℃/h is warming up to 400 ℃ with reactor, and constant temperature activated catalyst in 4 hours fully.After finishing the temperature of reactor is down to 200 ℃, begins to pump into above-mentioned cracked diesel oil, pump discharge is 100ml/h, then with the heating rate of 40 ℃/h the temperature of reactor is risen to 350 ℃, keeps this temperature sample analysis after 48 hours.Evaluation result sees Table 1.
Comparative example 1:
The commercial catalysts of catalyst for not passing through presulfurization outside the device that comparative example is used, to the used evaluating apparatus of its activity rating, amount of fill, raw material, experimental condition fully and embodiment 1,2,3,4 and 5 identical, just after packing reactor into, adopted by catalyst method for pre-sulphuration in the conventional device.
The above-mentioned commercial catalysts of 100ml is packed in the hydrogenation reactor, pass into hydrogen, Adjustment System pressure is 6.0MPa, and amounts of hydrogen is 800ml/min, with the heating rate of 35 ℃/h reactor is warming up to 120 ℃, and constant temperature made the catalyst dehydration in 2 hours.Dehydration begins to pump into presulfurization oil after finishing, and presulfurization oil is for having added the aviation kerosine of 3% carbon disulfide, and charging rate is 100ml/h.Then with the programming rate of 40 ℃/h the temperature of reactor is risen to 200 ℃, 240 ℃, 280 ℃, 320 ℃, and each temperature spot constant temperature 1 hour; Be warming up at last 340 ℃, kept 12 hours, make presulfiding of catalyst.Begin to pump into above-mentioned cracked diesel oil after finishing presulfurization, pump discharge is 100ml/h, then with the heating rate of 40 ℃/h the temperature of reactor is risen to 350 ℃, keeps this temperature sample analysis after 48 hours.Evaluation result sees Table 1.
Table 1 catalyst diesel oil hydrogenation activity rating table
| Project | Cracked diesel oil | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Catalyst | A | B | C | D | E | Commercial catalysts | |
| Reaction condition: | |||||||
| Temperature (℃) | 350 | 350 | 350 | 350 | 320 | 350 | |
| Hydrogen Vapor Pressure (MPa) | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | |
| Liquid air speed (h -1) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
| Hydrogen-oil ratio (V/V) | 480 | 480 | 480 | 480 | 480 | 480 | |
| Product characteristics: | |||||||
| Density (20 ℃, g/cm 3) | 0.893 | 0.853 | 0.863 | 0.860 | 0.873 | 0.865 | 0.870 |
| Aniline point (℃) | 49.0 | 59.0 | 59.0 | 60.2 | 60.2 | 55.2 | 61.0 |
| Sulfur content (μ g/g) | 6154 | 120 | 99 | 95 | 110 | 132 | 109 |
| Desulfurization degree (%) | 98.0 | 98.4 | 98.5 | 98.2 | 97.9 | 98.2 | |
| Nitrogen content (μ g/g) | 1035 | 81 | 61 | 70 | 60 | 89 | 60 |
| Denitrification percent (%) | 92.2 | 94.1 | 93.2 | 94.2 | 91.4 | 94.2 |
As can be seen from Table 1, the hydrogenation activity of the hydrogenation catalyst C that is obtained by embodiment 3 is best, and the hydrogenation activity of the catalyst A that obtains among all the other embodiment, B, D, E has has also met or exceeded the hydrogenation activity of Comparative Examples 1.Therefore outstanding advantages of the present invention be that pre-vulcanization process and equipment are simple, cost is low, easy to operate, on this basis, the presulfurization hydrogenation catalyst by method for pre-sulphuration production of the present invention can meet or exceed the effect of presulfurization in the device of complicated operation, cost costliness.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (11)
1. the outer method for pre-sulphuration of the device of a hydrogenation catalyst is characterized in that may further comprise the steps:
(a) the solution impregnation hydrogenation catalyst of usefulness thioacetamide and auxiliary agent thereof; Described hydrogenation catalyst be more than one metal by group vib metal molybdenum and/or tungsten and VIII family metallic cobalt and/or nickel as active component, and load on aluminium oxide and modifier thereof, molecular sieve, the activity carbon carrier with the form of oxide; Described auxiliary agent is selected from mercaptan, thiocarbamide, thiophene or polysulfide; The mol ratio of tenor is 0.5: 1 to 3: 1 in described thioacetamide and the described hydrogenation catalyst; The amount of described auxiliary agent is 0～50w% of described thioacetamide addition;
(b) the catalyst inert gas purge that above-mentioned steps is obtained.
2. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 1, it is characterized in that: said method can also comprise step (c), the catalyst that is about to obtain in the step (b) is packed in the reactor, heats up in hydrogen atmosphere and finishes sulfidation.
3. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 1 and 2, it is characterized in that: in described step (a), described solution is the aqueous solution or alcoholic solution.
4. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 3, it is characterized in that: described auxiliary agent is thiophene.
5. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 4, it is characterized in that: described inert gas is nitrogen.
6. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 1 and 2, it is characterized in that: the mol ratio of tenor is 0.5: 1 to 2: 1 in described thioacetamide and the described hydrogenation catalyst.
7. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 3, it is characterized in that: the content of described auxiliary agent is 10～30w% of described thioacetamide addition.
8. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 3, it is characterized in that: described alcohol is normal propyl alcohol.
9. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 8 is characterized in that: the temperature of the described hydrogenation catalyst of solution impregnation of described thioacetamide and auxiliary agent thereof is room temperature to 60 ℃, and dip time is 5～30 hours.
10. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 9 is characterized in that: described step (b) is under room temperature to 160 ℃, with nitrogen blowing 1～10 hour.
11. the outer method for pre-sulphuration of the device of hydrogenation catalyst according to claim 10, it is characterized in that: in described step (c), be under 200 ℃～500 ℃ the hydrogen atmosphere in temperature, with the catalyst treatment that obtains in the described step (b) 1～10 hour.
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| CN102527447B (en) * | 2010-12-27 | 2014-08-20 | 中国石油化工股份有限公司 | Ex-situ vulcanization method of catalyst for saturated hydrocarbon dehydrogenation |
| CN104525277A (en) * | 2014-12-09 | 2015-04-22 | 天津渤化永利化工股份有限公司 | Sulfurizing method of sulfur-tolerant shift catalyst |
| CN105709860B (en) * | 2014-12-20 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of vulcanization process of hydrogenation catalyst |
| CN104841493A (en) * | 2015-05-15 | 2015-08-19 | 中国石油大学(华东) | On-site external vulcanization processing method of hydrogenation catalysts |
| CN106179522B (en) * | 2016-07-08 | 2018-04-20 | 山东科技大学 | A kind of ex situ presulfiding method of hydrogenation catalyst |
| JP2020527103A (en) * | 2017-07-21 | 2020-09-03 | アルベマール ヨーロッパ エスアールエル | Hydrogenation catalyst containing titanium-containing carrier and sulfur-containing organic additive |
| CN113441188A (en) * | 2021-06-11 | 2021-09-28 | 中科合成油技术有限公司 | Pre-sulfurization method of inferior and/or heavy oil slurry bed hydrogenation iron-based catalyst |
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|---|---|---|---|---|
| CN1144836A (en) * | 1995-01-27 | 1997-03-12 | 法国石油公司 | Process for hydrogenating of diolefins and possibly olefins in hydrocarbon cuts which are rich in aromatic compounds using metallic catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144836A (en) * | 1995-01-27 | 1997-03-12 | 法国石油公司 | Process for hydrogenating of diolefins and possibly olefins in hydrocarbon cuts which are rich in aromatic compounds using metallic catalysts |
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