CN103769243B - The ex situ presulfiding method of hydrogenation catalyst - Google Patents
The ex situ presulfiding method of hydrogenation catalyst Download PDFInfo
- Publication number
- CN103769243B CN103769243B CN201210415053.0A CN201210415053A CN103769243B CN 103769243 B CN103769243 B CN 103769243B CN 201210415053 A CN201210415053 A CN 201210415053A CN 103769243 B CN103769243 B CN 103769243B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sulfur
- reduction pretreatment
- alcohol
- hydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of ex situ presulfiding method of hydrogenation catalyst, comprise the following steps: (1) oxidation state hydrogenation catalyst adopts alcohol to carry out reduction pretreatment; (2) mixture of sulfur-bearing agent introduced by the material after reduction pretreatment, then heat-treating.Compared with prior art, the inventive method can improve the hold sulphur rate of ex situ presulfiding catalyst, and improves catalyst serviceability.
Description
Technical field
The present invention relates to the method for the outer pre-sulfur vulcanization of a kind of hydrogenating catalyst.
Background technology
The hydrogenation catalysts such as hydrofinishing, hydrotreatment, hydrocracking generally contain the refractory oxides such as aluminium oxide, sial, molecular sieve as carrier, using molybdenum, tungsten, cobalt, nickel one or more as active metal component, sometimes can also contain the adjuvant components such as phosphorus, silicon, fluorine, titanium, zirconium, boron in catalyst.The metal component of the general catalyst obtained in process of production exists with oxidation state, and in hydrogenation process, and the active metal component of catalyst is in sulphided state, and (metal exists with oxide morphology: Co
9s
8, MoS
2, Ni
3s
2, WS
2deng) time there is higher reactivity worth, therefore, catalyst use before need to change its presulfurization into sulphided state.Thus, effect and the catalytic performance of presulfurization are in close relations, and the Method and Process of presulfurization controls all very important.
Prior art hydrogenation catalyst presulfurizing method mainly comprises two classes: in-situ presulfurization and ex situ presulfiding.In-situ presulfurization is that Catalyst packing is entered reactor, then introduces vulcanizing agent and carries out sulfuration, and this is the method comparatively often adopted, its weak point mainly the time longer, affect the production efficiency of process units.Before catalyst ex situ presulfiding refers to filling, catalyst has cured or vulcanizing agent exists, and is loaded into after in reactor without the need to introducing the method for vulcanizing agent.The major advantage of ex situ presulfiding is that device is short for on-stream time, improves the production efficiency of device.
Ex situ presulfiding technology changes the metal on catalyst into sulphided state completely, and then passivation uses; Or catalyst adds vulcanizing agent before being loaded into reactor, then in reactor, active metal is converted into sulphided state.Although this method preparation, storage, transport and filling are all comparatively easy, but the subject matter existed is that vulcanizing agent is difficult to fully act on catalyst metals, the pre-sulfide catalyst of sulfur-bearing agent is loaded in the activation process after reactor, easily causes vulcanizing agent to run off and the concentrated heat release of reaction.
The vulcanizing agent that the outer presulfurization of hydrogenating catalyst is selected generally comprises elemental sulfur, organic sulfur compound, inorganic sulphide and said mixture, and feed postition and processing method are had nothing in common with each other, and its presulfurization effect is also had nothing in common with each other.Because the cost of elemental sulfur is low, utilization rate is high, many technology use elemental sulfur to be vulcanizing agent.When using elemental sulfur, the mode in the prior art elemental sulfur being introduced catalyst generally comprises distillation absorption, fusing dipping, is dispersed in organic solution and floods, directly with solid elemental sulfur powder mixing etc.
USP4943547, USP5215954 etc. elemental sulfur is joined in higher boiling oil or organic solvent generate in advance suspension again with fresh catalyst effect, or with higher boiling, oily or organic solvent infiltrates after powdery elemental sulfur and contacts fresh catalyst.Said method can reach certain hold sulphur rate, but there is the problem concentrating heat release when catalyst activates in reactor, and hold sulphur rate also needs further raising.Elemental sulfur and organic sulfur dissolve in a solvent by USP6077803, simultaneously under stabilizing agent organic acid, mercaptan or organic alcohols existent condition, particularly under glycerine or hexose are stabilizing agent condition, element sulphur is introduced catalyst, but still there is concentrated exothermic phenomenon in weak point.
USP5786293, USP5821191, EP352851 etc. are vulcanizing agent with inorganic sulphide, generally adopt and elemental sulfur is dissolved in (NH
3)
2preparation method in S solution, its main deficiency is complicated operation, at least needs year sulfur content that double-steeping just can reach certain, and last drying must be carried out in an inert atmosphere.
The patents such as USP5017535, EP329499, USP4725569, EP130850 use the organic sulfur compound of mercaptan, dimethylsulphide, carbon disulfide and other carbon atoms 1-20 as vulcanizing agent.USP5922638, USP5397756 etc. use elemental sulfur and organic sulfur jointly as vulcanizing agent.Be large usage quantity by the subject matter of organic sulfurizing agent, price is high, and transport and filling process also exist some problems.
CN1107539C first uses hydrocarbon compound and catalyst exposure, then carries out ex situ presulfiding with hydrogen and sulfur-containing compound.Exist and higher temperature (embodiment is 330 DEG C) owing to there being hydrogen, sulfide decomposes generation hydrogen sulfide (in fact this patent directly uses hydrogen sulfide), metal reaction on hydrogen sulfide and catalyst generates metal sulfide, this belongs to the method for complete for catalyst presulfurization, the pre-sulfide catalyst obtained is easy to spontaneous combustion, in storage, transport and filling etc., there is safety problem.The oxygen-bearing organic matter coating pre-sulfide catalyst containing vulcanizing agent of CN1400056A containing at least 16 carbon atoms, a period of time is processed more than 175 DEG C, then Hydrogen activation is used, with reduce catalyst from heating problems, but can not solve completely sulphided state catalyst from heating problems, still there is certain problem in storage, the transport and filling etc. of catalyst.CN1262305A discloses a kind of hydrogenation catalyst presulfurizing method, and by vulcanization of rubber auxiliary agent, containing the mixing of olefin component, elemental sulfur and hydrogenation catalyst, vulcanization of rubber auxiliary agent promotes elemental sulfur and is combined containing olefin component, closes the loss of few sulphur.But do not solve the problem that activation process concentrates heat release.USP6059956(CN1076635C) with containing alkene or olefine fraction component as under vegetable oil exists, elemental sulfur and organic polysulfide are introduced catalyst, then Hydrogen activation is used, finally use oxygen-containing gas passivation, this patent claims passivation to improve catalyst activity, because metal on catalyst is sulphided state, still there is above-mentioned identical problem in this patent.CN200610046938.2 discloses a kind of preparation method of hydrogenating catalyst composition.Containing hydrogenation catalyst in composition, account for the organonitrogen compound of 0.5% ~ 20% of catalyst weight, account for the element sulphur that hydrogenation catalyst theory needs 30% ~ 150% of sulfur content, account for the organic solvent of 0.1% ~ 50% of catalyst weight.Preparation process introduces required material on oxidation state hydrogenation catalyst, then heat-treats in dynamic heat equipment.The method, by under introducing organonitrogen compound and sulphur, organic solvent acting in conjunction, can improving the hold sulphur rate of catalyst when activating further, slowing down concentrated heat release, the temperature rise of reduction beds, and can improve catalyst activity.The inventive method may be used for the processing procedure before the application of various hydrogenation catalyst.The method can improve hold sulphur rate and catalyst activity, but needs to improve further.
Summary of the invention
For the deficiencies in the prior art, the invention provides the outer method for pre-sulphuration of a kind of hydrogenating catalyst, hydrogenating catalyst composition of the present invention hold sulphur rate in activation process is high, and can improve the serviceabilities such as the activity of catalyst.
The outer method for pre-sulphuration of hydrogenating catalyst of the present invention comprises the following steps:
(1) oxidation state hydrogenation catalyst adopts alcohol to carry out reduction pretreatment, and the temperature of reduction pretreatment is 150 ~ 250 DEG C, and the time is 0.5 ~ 5 hour;
(2) mixture of sulfur-bearing agent introduced by the material after reduction pretreatment, then heat-treating.
In the inventive method, oxidation state hydrogenation catalyst can be conventional hydrogenation catalyst, as Hydrobon catalyst, hydrotreating catalyst, hydrocracking catalyst etc.General is carrier with refractory inorganic oxides, mixture etc. as aluminium oxide, silica, amorphous silicon aluminium, titanium oxide, molecular sieve and above-mentioned substance is carrier, active metal component is generally one or more in W, Mo, Ni and Co, auxiliary agent can be contained simultaneously, active metal component is oxidation state, i.e. WO
3, MoO
3, NiO and CoO.The selection of catalyst carrier for hydrgenating, active metal component and auxiliary agent and consumption can according to this area general knowledge according to application need specifically determine, for hydrocarbons hydrogenation catalyst, be generally 1% ~ 90% of catalyst weight with the hydrogenation metal component content of oxide basis, be generally 3% ~ 50%.
In the inventive method, alcohol carries out reduction pretreatment and uses the alcohol containing 2 ~ 8 carbon atoms, most preferably is one or more in ethanol, propyl alcohol, n-butanol, glycerine, sorbierite, xylitol, trihydroxy ethane, diethylene glycol (DEG), triethylene glycol, glycol and propane diols.Reduction pretreatment adopts alcohol or alcoholic solution oxide impregnation state catalyst, is then warming up to temperature requiredly to carry out reduction pretreatment.In the consumption of alcohol and catalyst, the atomic ratio of active metal component is 0.2:1 ~ 4:1.When using alcoholic solution to flood, before reduction pretreatment, can carry out desolvation step, at 50 ~ 120 DEG C by solvent removal, solvent can be that routine can dissolve the inorganic of alcohol or organic solvent.During the boiling point of pre-reduction treatment temperature higher than selected alcohol, select closed pressure resistant container to carry out pre-reduction treatment, avoid the loss of alcohol.
In the inventive method, vulcanizing agent comprises one or more in elemental sulfur, organic sulfur compound and inorganic sulphide, preferred elemental sulfur, and vulcanizing agent addition accounts for hydrogenation catalyst theory and needs 30% ~ 150% of sulfur content, is preferably 55% ~ 120%, most preferably 60% ~ 105%.In the mixture of sulfur-bearing agent, simultaneously containing organic solvent, organic solvent accounts for 0.1% ~ 50% of oxidized catalyst weight, and preferably 2% ~ 45%, more preferably 15% ~ 30%.Wherein hydrogenation catalyst theory needs sulfur content to be converted into sulfide (Co for institute's metallic components on catalyst
9s
8, MoS
2, Ni
3s
2, WS
2) time need the amount of sulphur.
Some organic solvents that organic solvent in the mixture of sulfur-bearing agent can adopt this area conventional, as one or more in hydrocarbon ils and organic carboxylic ester.Hydrocarbon ils generally can from one or more in the heavy end wet goods of various naphtha, gasoline, kerosene, diesel oil, white oil, lube base oil, straight run and decompression, the preferably hydrocarbon ils that obtains of secondary operations, as the above-mentioned hydrocarbon ils that the technique such as catalytic cracking, thermal cracking obtains.Organic carboxylic ester can be the organic carboxylic ester containing 6 ~ 60 carbon atoms, preferred fat acid glyceride, as sesame oil, safflower seed oil, corn oil, cottonseed oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut oil, olive oil, sunflower oil, lard, n-butyl acetate, 1-Methoxy-2-propyl acetate, 1, 4-butanediol diacrylate, cyclohexylenedinitrilotetraacetic acid isopropyl ester, hexa-methylene-1, 6 vulcabond, triethyl phosphate, methyl phenylacetate, isobutyl phenylacetate, terephthalic acid (TPA) dinonyl, repefral, diethyl phthalate, Methyl Salicylate, butyl p-hydroxybenzoate, and one or more in other organic carboxylic ester similar etc.Hydrocarbon ils, organic carboxylic ester can be used alone, also can be used in combination, if its weight ratio used in combination can be 1:15 ~ 15:1(hydrocarbon ils: organic carboxylic ester).Preferably used in combination, because can more be conducive to solving concentrated heat release problem.
In the inventive method, heat treatment process is preferably as follows process: at 100 ~ 130 DEG C, process 0 ~ 20h (hour), preferably 0.2 ~ 15h, at 130 ~ 180 DEG C, process 0.2 ~ 15h, at 180 ~ 300 DEG C, process 0 ~ 15h, preferably 1 ~ 8h.Absolute pressure can be adopted during heat treatment to be 0.05 ~ 1MPa pressure condition, generally can to carry out at ambient pressure.Heat treatment can be inert gas environment, and also can be oxygen content be 0.1v% ~ 30v% has oxygen atmosphere, can adopt flowing atmosphere, but generally not need forced flow atmosphere, adopt do not flow atmosphere or natural flow atmosphere.
The invention still further relates to the ex situ presulfiding catalyst that a kind of the inventive method obtains.
Hydrogenating catalyst composition of the present invention may be used for the various hydrogenation processes of various raw material, may be used for the unifining process, hydrocracking process, hydro-upgrading process etc. of hydro carbons according to the character of catalyst.Embody rule method comprises following content:
(A) hydrogenating catalyst composition of the present invention is loaded in reactor;
(B) will activate containing hydrogenation catalyst;
(C) under optimum conditions hydrocarbon raw material is contacted with hydrogenation catalyst with hydrogen, carry out the hydrogenation reaction of hydrocarbon raw material.
Activation condition described in step (B) is the activation condition of this area routine, generally comprises: pressure 1 ~ 20MPa, H
2air speed is 100 ~ 30000h
-1, programming rate 5 ~ 100 DEG C/h, reactor inlet final temperature is 200 ~ 400 DEG C, and constant temperature 2 ~ 36 hours at this temperature.Also can in the process of activation, any instant adds in the distillates such as gasoline, kerosene and diesel oil one or more, volume space velocity 0.2 ~ 20h during cut fluid
-1, H
2/ oil volume is than 100:1 ~ 2000:1.
Hydroconversion condition described in step (C) is the hydrogenation conditions of this area routine, different according to the difference of reacting, and is generally: pressure 1 ~ 20MPa, temperature 100 ~ 450 DEG C, H
2/ oil volume ratio is 50 ~ 3000, and during liquid, volume space velocity is 0.1 ~ 30h
-1.Described hydrocarbon raw material can be various hydrocarbon raw material, as gasoline fraction, kerosene distillate, diesel oil distillate, vacuum distillate or residual oil etc.
First carry out pre-reduction treatment in oxidation state hydrogenation catalyst of the present invention, effectively can improve the hold sulphur rate of vulcanizing agent in activation process, improve the serviceability of catalyst simultaneously, and solve concentrated heat release problem.Before drawing main vulcanizing agent, pre-reduction treatment is carried out to oxidized catalyst, improve the reagentia between active component and vulcanizing agent, improve the serviceability of hold sulphur rate and catalyst.
Detailed description of the invention
Select existing hydrogenation catalyst to carry out ex situ presulfiding process below, further illustrate process and the effect of the inventive method, but do not limit the scope of the invention.
Comparative example 1
Select the development of commercial oxidation state Hydrobon catalyst FH-5A(Fushun Petrochemical Research Institute, Wenzhou Hua Hua group company produces), main composition and character are in table 1.
Concrete presulfurization processing procedure is as follows:
1, evenly soaked by triethylamine and be loaded on oxidation state FH-5A catalyst, triethylamine addition is 9% of catalyst weight, obtains the catalyst of load triethylamine.
2, elemental sulfur is dispersed in catalytically cracked gasoline and rapeseed oil volume ratio is in the solvent of 5:1, solvent load is 25% of catalyst weight, elemental sulfur consumption is that catalyst containing metal theory needs 115% of sulfur content, the catalyst of the load triethylamine having disperseed the solvent of elemental sulfur to spray to obtain in step 1.
3, the catalyst that obtains of step 2 is in normal pressure, not moving air atmosphere, process 4 hours at 165 DEG C, obtains ex situ presulfiding catalyst B-1.
Comparative example 2
Oxidized catalyst is identical with embodiment 1, is FH-5A.
Concrete presulfurization processing procedure is as follows:
1, triethylamine and grape acid are dissolved in the ammoniacal liquor containing ammonia 10wt% by weight 5:1, by this solution impregnation oxidized catalyst, above-mentioned substance consumption is 7% of catalyst weight, then at 120 DEG C dry 5 hours, obtains the catalyst containing mixing organics additive.
2, elemental sulfur is dispersed in vacuum distillate and peanut oil volume ratio is in the solvent of 1:3, solvent load is 30% of catalyst weight, elemental sulfur consumption is that catalyst containing metal theory needs 90% of sulfur content, on the catalyst that the step 1 of having disperseed the solvent of elemental sulfur to spray to obtain in step 1 obtains.
3, the catalyst that obtains of step 2 is in normal pressure, flow of nitrogen gas atmosphere (nitrogen amount 50L/L catalyst hour), process 2 hours at process 4 hours, 270 DEG C at 140 DEG C, obtains ex situ presulfiding catalyst B-2.
Comparative example 3
By the method for comparative example 2, cancel the 1st step, the 2nd step is identical with embodiment 2, obtains ex situ presulfiding catalyst B-3.
Get the oxidized catalyst of comparative example 1, carry out ex situ presulfiding process as follows.
(1) oxidation state hydrogenation catalyst adopts n-butanol to carry out reduction pretreatment, n-butanol consumption is the mol ratio of active metal atom in catalyst is 1:1, n-butanol is impregnated in oxidized catalyst, then in closed container, reduction pretreatment is carried out, the temperature of reduction pretreatment is 160 DEG C, and the time is 3 hours;
(2) mixture of sulfur-bearing agent introduced by the material after reduction pretreatment, vulcanizing agent is sulphur, sulphur is dispersed in catalytically cracked gasoline and rapeseed oil volume ratio is in the solvent of 5:1, solvent load is 25% of oxidized catalyst weight, sulfur consumption is that catalyst containing metal theory needs 115% of sulfur content, on the catalyst having disperseed the solvent of sulphur to spray after step (1) processes.Then heat-treating, heat treatment, in normal pressure, not moving air atmosphere, process 4 hours at 165 DEG C, obtains ex situ presulfiding catalyst A-1.
Comparative example 4
Compared with embodiment 1, cancellation step (1), the n-butanol of same amount adds in the mixture of the sulfur-bearing agent in step (2), and other condition, with embodiment 1, obtains ex situ presulfiding catalyst B-4.
Embodiment 2
Get the oxidized catalyst of comparative example 1, carry out ex situ presulfiding process as follows.
(1) oxidation state hydrogenation catalyst adopts sorbierite to carry out reduction pretreatment, n-butanol consumption is the mol ratio of active metal atom in catalyst is 0.8:1, n-butanol is made into the aqueous solution that mass concentration is 30%, then be impregnated in oxidized catalyst, moisture is removed 120 DEG C of dryings, then carry out reduction pretreatment, the temperature of reduction pretreatment is 220 DEG C, and the time is 1 hour;
(2) mixture of sulfur-bearing agent introduced by the material after reduction pretreatment, vulcanizing agent is sulphur, sulphur is dispersed in catalytic cracking diesel oil, solvent load is 15% of oxidized catalyst weight, sulfur consumption is that catalyst containing metal theory needs 105% of sulfur content, on the catalyst having disperseed the solvent of sulphur to spray after step (1) processes.Then heat-treating, heat treatment, in normal pressure, not moving air atmosphere, process 6 hours at 155 DEG C, obtains ex situ presulfiding catalyst A-2.
Embodiment 3
Get the oxidized catalyst of comparative example 1, carry out ex situ presulfiding process as follows.
(1) oxidation state hydrogenation catalyst adopts diethylene glycol (DEG) to carry out reduction pretreatment, diethylene glycol (DEG) consumption is the mol ratio of active metal atom in catalyst is 2:1, diethylene glycol (DEG) is made into the aqueous solution that mass concentration is 15%, then be impregnated in oxidized catalyst, moisture is removed 120 DEG C of dryings, then carry out reduction pretreatment, the temperature of reduction pretreatment is 180 DEG C, and the time is 2 hours;
(2) mixture of sulfur-bearing agent introduced by the material after reduction pretreatment, vulcanizing agent is sulphur, sulphur is dispersed in soybean oil, soybean oil consumption is 20% of oxidized catalyst weight, sulfur consumption is that catalyst containing metal theory needs 110% of sulfur content, on the catalyst having disperseed the solvent of sulphur to spray after step (1) processes.Then heat-treating, heat treatment, in normal pressure, not moving air atmosphere, process 5 hours at 120 DEG C, processes 4 hours at 165 DEG C, processes 1 hour, obtain ex situ presulfiding catalyst A-3 at 220 DEG C.
Embodiment 4
Get the oxidized catalyst of comparative example 1, carry out ex situ presulfiding process by embodiment 1 same steps.Just in step (1), n-butanol ethanol replaces.Finally obtain ex situ presulfiding catalyst A-4.
Embodiment 5
Get the oxidized catalyst of comparative example 1, carry out ex situ presulfiding process by embodiment 3 same steps.Just in step (1), n-butanol ethanol replaces.Finally obtain ex situ presulfiding catalyst A-5.
The hydrogenation catalyst of the sulfur-bearing agent that the various embodiments described above and comparative example obtain carries out hold sulphur rate and activation process.Hold sulphur rate test condition is: pressure 5.0MPa, temperature 150 DEG C, H
2/ diesel oil (character is in table 3) volume ratio is 400, and during liquid, volume space velocity is 3.5h
-1, constant temperature 6 hours.Hold sulphur rate is the percentage by weight that the sulphur retained after above-mentioned process accounts for initial sulphur.Concrete outcome is in table 2.
Each embodiment and comparative example obtain sulfur-bearing agent hydrogenation catalyst activated process and condition is: carry out in fixed bed reactors, and catalyst bed layer height is 800mm, and activation condition is: pressure 2MPa, hydrogen-oil ratio 500, activation oil (diesel oil) liquid hourly space velocity (LHSV) 3h
-1, programming rate 30 DEG C/h, final intensification 300 DEG C, constant temperature time 12h.Contrast on effect when embodiment and comparative example ex situ presulfiding catalyst are used for diesel oil fraction hydrogenating is in table 4.
Table 1FH-5A Hydrobon catalyst mainly forms and character.
| Catalyst | Oxidation state FH-5A |
| Carrier | Al 2O 3 |
| Active metal composition/wt% | |
| MoO 3 | 24.3 |
| NiO | 4.2 |
| Auxiliary agent SiO 2 /wt% | 10.1 |
| Pore volume/mlg -1 | 0.4 |
| Specific area/m 2·g -1 | 190 |
Table 2 embodiment and comparative example sulfur-bearing agent hydrogenation catalyst hold sulphur rate.
| Sequence number | Pre-sulfide catalyst | Hold sulphur rate, % |
| Comparative example 1 | B-1 | 62.9 |
| Comparative example 2 | B-2 | 68.5 |
| Comparative example 3 | B-3 | 52.6 |
| Comparative example 4 | B-4 | 78.9 |
| Embodiment 1 | A-1 | 92.7 |
| Embodiment 2 | A-2 | 91.4 |
| Embodiment 3 | A-3 | 95.8 |
| Embodiment 4 | A-4 | 91.7 |
| Embodiment 5 | A-5 | 96.0 |
The test of table 3 hold sulphur rate and activation process diesel oil character.
| Feedstock oil | Diesel oil |
| Density (20 DEG C)/kgm -3 | 830.5 |
| The end point of distillation/DEG C | 352 |
| Sulphur/μ gg -1 | 687 |
| Nitrogen/μ gg -1 | 116.7 |
| Acidity/mgKOH (100mL) -1 | 5.53 |
Table 4 is for the condition of diesel oil fraction hydrogenating and effect.
| Catalyst title | A-1 | B-4 | |
| Raw material and product | Catalytic cracking diesel oil | Refined oil | Refined oil |
| Reaction temperature/DEG C | 340 | 340 | |
| Reaction pressure/MPa | 6.0 | 6.0 | |
| Hydrogen-oil ratio | 350 | 350 | |
| Volume space velocity/h -1 | 3.0 | 3.0 | |
| The end point of distillation/DEG C | 355 | 354 | 354 |
| Sulphur/μ gg -1 | 10766 | 420 | 3170 |
As can be seen from the data of embodiment and comparative example, during the ex situ presulfiding catalyst activation that the present invention program obtains, there is higher hold sulphur rate, and there is more outstanding catalytic activity.
Claims (18)
1. an ex situ presulfiding method for hydrogenation catalyst, is characterized in that comprising the following steps:
(1) oxidation state hydrogenation catalyst adopts alcohol to carry out reduction pretreatment, and the temperature of reduction pretreatment is 150 ~ 250 DEG C, and the time is 0.5 ~ 5 hour;
(2) mixture of sulfur-bearing agent introduced by the material after reduction pretreatment, and then heat-treats;
Wherein, alcohol carries out the alcohol of reduction pretreatment use containing 2 ~ 8 carbon atoms; In the consumption of alcohol and catalyst, the atomic ratio of active metal component is 0.2:1 ~ 4:1.
2. method according to claim 1, is characterized in that: oxidation state hydrogenation catalyst comprises hydrotreating catalyst or hydrocracking catalyst.
3. method according to claim 1, is characterized in that: alcohol carries out one or more in reduction pretreatment use ethanol, propyl alcohol, n-butanol, glycerine, sorbierite, xylitol, trihydroxy ethane, diethylene glycol (DEG), triethylene glycol, glycol and propane diols.
4. method according to claim 1, is characterized in that: reduction pretreatment adopts alcohol or alcoholic solution oxide impregnation state catalyst, is then warming up to temperature requiredly to carry out reduction pretreatment.
5. method according to claim 4, is characterized in that: when using alcoholic solution to flood, before reduction pretreatment, carry out desolvation step, at 50 ~ 120 DEG C by solvent removal, solvent is that routine can dissolve the inorganic of alcohol or organic solvent.
6. method according to claim 1, is characterized in that: vulcanizing agent comprises one or more in elemental sulfur, organic sulfur compound and inorganic sulphide, and vulcanizing agent addition accounts for hydrogenation catalyst theory and needs 30% ~ 150% of sulfur content.
7. method according to claim 6, is characterized in that: vulcanizing agent is elemental sulfur.
8. method according to claim 6, is characterized in that: vulcanizing agent addition accounts for hydrogenation catalyst theory and needs 55% ~ 120% of sulfur content.
9. method according to claim 6, is characterized in that: vulcanizing agent addition accounts for hydrogenation catalyst theory and needs 60% ~ 105% of sulfur content.
10. the method according to claim 1 or 6, is characterized in that: in the mixture of sulfur-bearing agent, and simultaneously containing organic solvent, organic solvent accounts for 0.1% ~ 50% of oxidized catalyst weight.
11. methods according to claim 10, is characterized in that: organic solvent accounts for 2% ~ 45% of oxidized catalyst weight.
12. methods according to claim 10, is characterized in that: organic solvent accounts for 15% ~ 30% of oxidized catalyst weight.
13. methods according to claim 10, is characterized in that: the organic solvent in the mixture of sulfur-bearing agent is one or more in hydrocarbon ils and organic carboxylic ester.
14. methods according to claim 1, is characterized in that: heat treatment process processes 0 ~ 20h at 100 ~ 130 DEG C, at 130 ~ 180 DEG C, process 0.2 ~ 15h, at 180 ~ 300 DEG C, process 0 ~ 15h.
15. methods according to claim 1, is characterized in that: heat treatment process processes 0.2 ~ 15h at 100 ~ 130 DEG C, at 130 ~ 180 DEG C, process 0.2 ~ 15h, at 180 ~ 300 DEG C, process 1 ~ 8h.
16. methods according to claim 14, is characterized in that: heat treatment adopts absolute pressure to be 0.05 ~ 1MPa pressure condition.
17. method according to claim 1, is characterized in that: heat treatment is inert gas environment, or oxygen content be 0.1v% ~ 30v% have oxygen atmosphere.
The ex situ presulfiding catalyst that method according to any one of 18. claims 1 to 17 obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210415053.0A CN103769243B (en) | 2012-10-26 | 2012-10-26 | The ex situ presulfiding method of hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210415053.0A CN103769243B (en) | 2012-10-26 | 2012-10-26 | The ex situ presulfiding method of hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769243A CN103769243A (en) | 2014-05-07 |
| CN103769243B true CN103769243B (en) | 2016-04-27 |
Family
ID=50562275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210415053.0A Active CN103769243B (en) | 2012-10-26 | 2012-10-26 | The ex situ presulfiding method of hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769243B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179522B (en) * | 2016-07-08 | 2018-04-20 | 山东科技大学 | A kind of ex situ presulfiding method of hydrogenation catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681756A (en) * | 2002-09-17 | 2005-10-12 | 约翰森·马瑟公开有限公司 | Process for production of an alcohol |
| CN102041045A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | On-stream method of residual oil hydrogenation process |
-
2012
- 2012-10-26 CN CN201210415053.0A patent/CN103769243B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681756A (en) * | 2002-09-17 | 2005-10-12 | 约翰森·马瑟公开有限公司 | Process for production of an alcohol |
| CN102041045A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | On-stream method of residual oil hydrogenation process |
Non-Patent Citations (1)
| Title |
|---|
| 金属纳米颗粒制备中的还原剂与修饰剂;王立英等;《化学进展》;20100430;第22卷(第4期);第581页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769243A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100360236C (en) | Treatment method before application of hydrogenation catalyst | |
| CN100525913C (en) | Process of treating hydrogenation catalyst before application | |
| CN101417245B (en) | Hydrogenation catalyst processing method | |
| CN102465008B (en) | Sulfuration method of catalyst for hydrocracking technology | |
| CN101417230B (en) | Processing method before applying hydrogenation catalyst | |
| CN103059910B (en) | Vulcanization method of hydrofining catalyst | |
| CN103059968B (en) | Vulcanization startup method of hydrocracking device | |
| CN100525912C (en) | Treatment method before application of hydrogenation catalyst | |
| CN101088616B (en) | Process of treating hydrogenation catalyst before application | |
| CN102051204B (en) | Work starting method for hydrogenation process | |
| CN100360237C (en) | Sulfurized hydrogenation catalyst, prepn. method | |
| CN100413587C (en) | Sulfurized type catalyst, and its prepn. method | |
| CN103059940B (en) | The start-up method of hydroeracking unit | |
| CN101148607B (en) | Hydrocarbon hydroprocessing technique | |
| CN100360231C (en) | Hydrogenating catalyst composition and preparation process thereof | |
| CN102041044B (en) | On-stream method of residual oil hydrogenation process | |
| CN102041045B (en) | On-stream method of residual oil hydrogenation process | |
| CN101148608B (en) | Hydrocarbon hydroprocessing technique | |
| CN103769243B (en) | The ex situ presulfiding method of hydrogenation catalyst | |
| CN102051203B (en) | Start-up method for external presulfurizing catalyst | |
| CN102311765B (en) | Startup sulfurization method for trickle bed class-II active center hydrogenation catalyst | |
| CN109794265A (en) | Sulfurized hydrogenation catalyst for refining and preparation method thereof, fraction oil hydrogenation refining method | |
| CN103769242B (en) | A kind of ex situ presulfiding method of hydrogenation catalyst | |
| CN101417246A (en) | Processing method before using hydrogenation catalyst | |
| CN101088620A (en) | Prepn process of vulcanized catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |