CN1115384C - Process for presulfurizing hydrocatalyst - Google Patents
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- CN1115384C CN1115384C CN 00129837 CN00129837A CN1115384C CN 1115384 C CN1115384 C CN 1115384C CN 00129837 CN00129837 CN 00129837 CN 00129837 A CN00129837 A CN 00129837A CN 1115384 C CN1115384 C CN 1115384C
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Abstract
The present invention relates to a prevulcanization method of a hydrogenation catalyst, which comprises: vulcanized oil containing a vulcanizing agent contacts a hydrogenation catalyst in an oxidation state under the prevulcanization condition; subsequently, the vulcanized oil contacts a hydrogen containing gas at the temperature of 230 to 450DEG C, the contact time is at least 0.5 hour, and the flow quantity of the hydrogen containing gas is at least 5 milliliters of hydrogen per hour in every one gram of catalyst. The carbon deposition quantity of the catalyst can be obviously reduced by prevulcanizing the hydrogenation catalyst with the method provided by the present invention so that the activity stability of the catalyst is improved.
Description
The invention relates to a kind of method for pre-sulphuration of hydrogenation catalyst.
Hydrogenation catalyst comprises numerous species; as being the purpose Hydrobon catalyst with desulfurization, denitrogenation; with desulfurization, denitrogenation, deolefination, take off the hydrotreating catalyst that aromatic hydrocarbons is purpose; with demetalization, colloid and other impurity is the agent of purpose hydrogenation protecting, is hydrocracking catalyst of purpose or the like to produce oil fuel.These catalyzer all contain a kind of support of the catalyst and the group vib hydrogenation active metals and the group VIII hydrogenation active metals that load on this carrier.Group vib hydrogenation active metals commonly used is molybdenum and/or tungsten, and group VIII hydrogenation active metals commonly used is nickel and/or cobalt.The support of the catalyst of Hydrobon catalyst, hydrogenation protecting catalyst generally is selected from heat-resistant inorganic oxide.The carrier of hydrocracking catalyst generally is selected from a kind of carrier that contains zeolite and heat-resistant inorganic oxide.The carrier of hydrotreating catalyst promptly can be a heat-resistant inorganic oxide, also can be the mixture of zeolite and heat-resistant inorganic oxide.
Group vib hydrogenation active metals in the hydrogenation catalyst, as molybdenum and/or tungsten, the group VIII hydrogenation active metals, as nickel and/or cobalt, before use, all the form with oxidation state is present in the catalyzer, in hydroconversion process, though owing to contain sulfide in the stock oil, change into sulphided state by reaction, but because under reaction conditions, sulphur content is low excessively in the stock 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 prevulcanized.
The method of hydrogenation prevulcanized is divided into two big classes substantially, i.e. the outer prevulcanized method of prevulcanized method and device in the device.
The prevulcanized method is a kind of traditional method for pre-sulphuration in the device, and it comprises gas phase prevulcanized method and liquid phase prevulcanized method again.The prevulcanized method has been conventionally known to one of skill in the art in the device, to this, " Chinese oil Refining Technologies ", and the Hou Xianglin chief editor, Sinopec press, 279-281,1991, done comparatively detailed summary.
The outer prevulcanized method of device has also had many reports.
US4,177,136 disclose a kind of hydroprocessing process of hydrocarbon raw material, described hydrocarbon raw material contains and has carbon-sulfide linkage, the compound of carbon-nitrogen bond and carbon-oxygen bond, described hydroprocessing process is included under the temperature of raising, hydrocarbon raw material and hydrogen are contacted with a kind of hydrotreating catalyst to remove sulphur wherein, nitrogen and oxygen, its improvement is to have used a kind of sulfurized catalyzer, described catalyzer is metal oxide-loaded catalyzer to be carried out prevulcanized as follows obtain: under the condition that does not have hydrogen to exist, the catalyzer of load hydrogenation metal oxide compound is contacted with elementary sulfur, at least a portion of described elementary sulfur is entered in the hole of catalyzer, contact with hydrogen at the 200-600 ℃ of catalyzer that will introduce sulphur.
EP359,356A1 have proposed the method for pre-sulphuration of two kinds of hydrotreating catalysts.A kind of method comprises that (1) under the temperature that is lower than 210 (about 99 ℃), contacts catalyzer with pulverous elementary sulfur, and described elementary sulfur is entered in the hole of catalyzer basically, forms a kind of mixture; And (2) in the presence of hydrogen with described mixture heating up to more than the fusing point of sulphur to 390 °F (about 199 ℃).Another kind method comprises that (1) under the temperature that is lower than 210 (about 99 ℃), contacts catalyzer with pulverous elementary sulfur, and described elementary sulfur is entered in the hole of catalyzer basically, forms a kind of mixture; And (2) described mixture is mixed with at least a material that is selected from varsol and high boiling point oil, form a kind of wetting in advance mixture, this method can also comprise described wet mix in advance is heated to more than the fusing point of sulphur.
US5,215,954 disclose the method for two kinds of prevulcanized containing metal oxide catalysts, first method comprises (1) method with distillation and/or fusing, described catalyzer is contacted with elementary sulfur, the temperature of contact enters in the hole of catalyzer described elementary sulfur basically, (2) in the presence of liquid olefin, temperature approximately greater than 150 ℃ condition under the catalyzer of heating introducing sulphur.Second method comprises the mixture of described catalyzer with Powdered elementary sulfur and liquid olefin contacted, and more than the mixture to 150 that obtains of heating ℃.
US5,139,990 disclose a kind of Preparation of catalysts method that is used for the raw material of hydrocarbon-containifirst is carried out hydrotreatment, this method comprises that (1) obtains a kind of catalyzer, this catalyzer contains a kind of solid support material, and this solid support material deposits one or more raw materials to hydrocarbon-containifirst and carries out activated metal of hydrotreatment or metallic compound; (2) contact with the catalyzer of step (1) with the liquid medium that contains organosulfur compound, in catalyzer, introduce the organic sulfide of significant quantity, described organosulfur compound is selected from following one group: the salt of ethylenebis (dithiocarbamic acid), 2,5-dimercapto-1,3, the salt of 4-thiadiazoles, thiocarbamide, ammonium sulfocyanate, dimethyl sulfoxide (DMSO), 3,4-dithia adipate, 2,2-dithio glycol.
US5,681,787 disclose a kind of hydrogenation catalyst particulate method for pre-sulphuration that contains at least a metal or metal oxide, this method comprises that (1) contacts described catalyzer with elementary sulfur, the temperature of contact makes to small part sulphur and enters in the hole of catalyzer, and (2) described catalyzer is contacted with at least a oxygen-containing hydrocarbon class with at least 12 carbon atoms, obtain a kind of catalyzer with self-heating character of reduction.
CN85,107,953A discloses a kind of method for pre-sulphuration of catalyzer, this catalyzer contains at least a metal or nonmetal oxide carrier and at least a active metal, in first step of reaction, under the no hydrogen condition, at 0-50 ℃, handle this catalyzer with at least a vulcanizing agent, make this vulcanizing agent partly or entirely penetrate in the catalyst pores, this vulcanizing agent is the polysulfide with following chemical general formula: R-S (n)-R ', n is 3-20 in the formula, R ' expression hydrogen atom or other groups identical or inequality with the R group, these two kinds of groups represent to have the organic group of 1-150 carbon atom respectively, and these groups are selected from full and/or undersaturated straight chain, side chain or annular alkyl group, aromatic yl group, alkylaryl group and aromatic base alkyl group, vulcanizing agent is dissolved in the solvent and uses, and catalyzer is carried out drying treatment.Then in second step of reaction, the catalyzer that first step of reaction was handled is handled in order to method down: (1) do not have hydrogen to exist and an inertia is arranged or condition that non-rare gas element exists under, under the pressure of 65-275 ℃ temperature and 0.5-70 crust, times processing catalyzer with at least 5 minutes, (2) are under at least 275 ℃ temperature, with the further catalyzer of handling of at least 1 minute time then.
CN1,082,591A1 discloses the method that a kind of processing contains the catalyzer of at least a metal or nonmetal oxide and at least a reactive metal, this method is to handle catalyzer with at least a vulcanizing agent, described vulcanizing agent is selected from one group that is made up of elementary sulfur and the organic sulfide with R-S (n)-R ' chemical formula, n is 3-20 in the formula, R and R ' can be the same or different, the molecule of each group has 1-150 carbon atom, be selected from by saturated or undersaturated straight or branched or alkane type alkyl, aryl, in the group that alkaryl and aralkyl are formed, R ' can also represent hydrogen atom.
Activity through the sulfurized hydrogenation catalyst is improved, still, along with the raising of catalyst activity, the also easier carbon deposit of catalyzer, thus catalyst deactivation speed is increased.
People such as M.Marafi (Applied CatalysisA:General 159,259-267,1997) are raw material with the vacuum gas oil, to sulphided state Ni-Mo/ γ-Al
2O
3Desulfurization, the denitrification reaction of hydrotreating catalyst are studied, find that the carbon deposit process mainly occurs in the initial stage of reaction, reacting at the beginning, carbon deposit just forms fast, react in 3 hours, coke content promptly reaches 10 heavy %, reaction times, the coke content on the catalyzer reached balance in 24 hours.
Since the carbon deposit process mainly occurs in the initial stage of reaction, thereby make catalyst deactivation, if can control the coke content of hydrogenation catalyst in initial reaction stage, the deactivation rate of catalyzer can reduce greatly, and adopts existing method for pre-sulphuration not address this problem.
The purpose of this invention is to provide and a kind ofly new can reduce the hydrogenation catalyst coke content, reduce the method for pre-sulphuration of the hydrogenation catalyst of catalyst deactivation speed.
Method provided by the invention is included under the prevulcanized condition, a kind of vulcanized oil of Containing Sulfur agent is contacted with a kind of oxidation state hydrogenation catalyst, it is characterized in that, this method also comprises and will contact with a kind of gas of hydrogen with catalyzer after vulcanized oil contacts, the described temperature that contacts with the gas of hydrogen is 230-450 ℃, be at least 0.5 hour duration of contact, and the flow of the gas of hydrogen is per hour at least 5 milliliters of hydrogen of every gram catalyzer.
According to method provided by the invention, the gas of described hydrogen can be pure hydrogen, also can be the gas mixture of hydrogen and rare gas element.In the gas mixture of described hydrogen and rare gas element, the content of hydrogen is arbitrarily, if the flow of gas mixture can guarantee every gram catalyzer per hour at least 5 milliliters of hydrogen can reach purpose of the present invention.Because hydrogen content is low excessively in the gas mixture, the consumption of required gas mixture is too big, therefore, and preferred pure hydrogen or the hydrogen of hydrogen content at least 80 body % and the gas mixture of rare gas element of the gas of described hydrogen.Rare gas element described here is selected under described contact conditions, not with the gas of catalyzer, hydrogen generation chemical action in one or more.These rare gas elementes include but not limited to the rare gas element of zero group in nitrogen, the periodic table of elements etc.Wherein, be preferably nitrogen.
The temperature that catalyzer described and after vulcanized oil contacts contacts with a kind of atmosphere of hydrogen is preferably 300-420 ℃.Be preferably 1-50 hour duration of contact, more preferably 5-50 hour.The flow of the gas of described hydrogen can be very big, but in order to economize on resources, be preferably per hour 5-5000 milliliter hydrogen of every gram catalyzer, and more preferably every gram catalyzer is 100-3000 milliliter hydrogen per hour.
According to method provided by the invention, the pressure that catalyzer described and after vulcanized oil contacts contacts with the gas of hydrogen does not have special requirement, and described contact can be carried out under the pressure of normal pressure to 15 MPa.
According to method provided by the invention, described under the prevulcanized condition, promptly is wet method pre-vulcanization process of the prior art with a kind of vulcanized oil of Containing Sulfur agent with contacting of a kind of oxidation state hydrogenation catalyst, and the contact conditions of the used vulcanized oil of this process, vulcanizing agent and catalyzer and vulcanized oil has been conventionally known to one of skill in the art.Described vulcanized oil is selected from one or more in the various vulcanized oils that can be used for the wet method prevulcanized, as in kerosene, solar oil, atmosphere 3rd side cut distillate, decompression two wires distillate, reduce pressure three-way distillate, catalytic cracking diesel oil, the coker gas oil one or more, wherein, preferred kerosene or solar oil.Described vulcanizing agent is selected from one or more in the various vulcanizing agents that can be used for the wet method prevulcanized, as hydrogen sulfide, dithiocarbonic anhydride, mercaptan, thiophene and derivative thereof, dialkyl sulfide, as dimethylsulphide, in the dimethyl thioether etc. one or more, wherein, preferred hydrogen sulfide, dithiocarbonic anhydride or dimethyl thioether.The content of vulcanizing agent in vulcanized oil is the heavy % of 0.1-10, is preferably the heavy % of 1-5.The condition that described vulcanized oil contacts with catalyzer is preferably 250-320 ℃ for 230-350 ℃ of contact temperature, and contact pressure 0.1-15 MPa is preferably the 1-12 MPa, and hydrogen to oil volume ratio is 50-2000, is preferably 100-1000, and liquid hourly space velocity is 0.5-10 hour
-1, be preferably 1-4 hour
-1, at least 0.5 hour duration of contact, be preferably 2-48 hour.
Described oxidation state hydrogenation catalyst comprises Hydrobon catalyst, hydrotreating catalyst, hydrogenation protecting agent that contains oxidation state group vib and group VIII hydrogenation active metals and heat-resistant inorganic oxide carrier and hydrotreating catalyst or the hydrocracking catalyst that contains zeolite, heat-resistant inorganic oxide and group vib and group VIII hydrogenation active metals.Wherein, preferred molybdenum of described group vib hydrogenation active metals and/or tungsten, the group VIII hydrogenation active metals is preferably nickel and/or cobalt.
In described hydrogenation catalyst, described heat-resistant inorganic oxide is selected from one or more in the heat-resistant inorganic oxide that is commonly used for catalyst carrier for hydrgenating or matrix.As in aluminum oxide, silicon oxide, titanium oxide, zirconium white, the boron oxide one or more, preferred heat-resistant inorganic oxide is aluminum oxide and/or silicon oxide.
Zeolite in described hydrotreatment or the hydrocracking catalyst is selected from one or more in the zeolite that is commonly used for hydrotreating catalyst or hydrocracking catalyst active ingredient, generally speaking, be selected from mesopore and the large pore zeolite one or more, as in y-type zeolite, Beta zeolite, the ZSM-5 zeolite one or more.
In described hydrogenation catalyst, can also contain the adjuvant component that hydrogenation catalyst usually contains, these adjuvant components are selected from fluorine, magnesium, phosphorus, in the periodic table of elements in VB family element, VIIB family element, IB family element, IIB family element, tin, antimony, bismuth and the tellurium one or more, wherein, fluorine, magnesium or phosphorus are the most commonly used.
Adopt method provided by the invention can obviously reduce the coke content on the hydrogenation catalyst in the hydrogenation process, activity of such catalysts stability is improved.For example, weigh % according to method provided by the invention to containing nickel oxide 2.0, tungsten fluoride 21.2 heavy %, after the Hydrobon catalyst of fluorine 4.4 heavy % and surplus alumina supporter carries out prevulcanized, at 320 ℃, 3.2 MPa, hydrogen to oil volume ratio is 500, liquid hourly space velocity is under 2.0 hours-1 the condition, to nitrogenous 916ppm, the catalytic diesel oil of sulphur 5200ppm carries out hydrofining, react after 300 hours, carbon deposit content only is 2.1 heavy % on the catalyzer, denitrification percent reaches 53.87 heavy %, desulfurization degree reaches 89.42 heavy %, and adopts traditional method for pre-sulphuration, and other condition and catalyzer homogeneous phase are simultaneously, react after 270 hours, carbon deposit content is just up to 4.8 heavy % on the catalyzer, and denitrification percent has only 45.36 heavy %, and desulfurization degree has only 86.52 heavy %.
The following examples will the present invention will be further described.
Example 1
Following example illustrates method for pre-sulphuration provided by the invention.
Press CN85,104, the method of 438B example 3 prepares Hydrobon catalyst, the nickel oxide 2.0 that consists of of catalyzer weighs %, Tungsten oxide 99.999 21.2 heavy %, fluorine 4.4 heavy %, surplus is an aluminum oxide, it is the bar of 1-2 millimeter that the catalyst breakage that obtains is become length, and 100 milliliters of the catalyzer after the fragmentation are packed in the reactor of medium-sized trickle bed reaction unit, feeds the virgin kerosene that contains dithiocarbonic anhydride 2 heavy %, (it is as shown in the table for the character of virgin kerosene), 290 ℃ of temperature, hydrogen dividing potential drop 3.2 MPas, liquid hourly space velocity 2.0 hours
-1, hydrogen to oil volume ratio is under 200 the condition, the described virgin kerosene that contains dithiocarbonic anhydride 2 heavy % to be contacted 12 hours with catalyzer.Then, stop to enter the virgin kerosene that contains dithiocarbonic anhydride, be warming up to 300 ℃, simultaneously, regulating hydrogen flowing quantity is per hour 400 milliliters of every gram catalyzer, and constant temperature was handled 30 hours.Introduce the catalytic diesel oil shown in the table 1, catalytic diesel oil is carried out hydrofining, purification condition is 320 ℃ of temperature of reaction, hydrogen dividing potential drop 3.2 MPas, liquid hourly space velocity 2.0 hours
-1, hydrogen to oil volume ratio 500.The reaction operation was stopped work after 300 hours, the sulphur of analysed preparation oil, nitrogen content, and calculate denitrification percent and desulfurization degree, the results are shown in Table 2.Catalyzer being drawn off from reactor, get 20 gram samples, is that solvent carries out the Soxhlet extracting with toluene, and the carbon deposit content in the catalyzer is measured in the oven dry back, and the results are shown in Table 2.Wherein, sulphur content adopts sh/T 0253-92 method to measure, and nitrogen content has been adopted chemiluminescence determination, and the carbon deposit content assaying method is referring to " petrochemical complex analytical procedure (RIPP test method) ", Science Press, P302,1990.
Comparative Examples 1
Method by example 1 is carried out hydrofining to same stock oil, different just with after the virgin kerosene that contains dithiocarbonic anhydride 2 heavy % contact, directly introduce catalytic diesel oil, the process that the catalyzer after vulcanizing contacts with hydrogen, in 270 hours reaction times, the result is as shown in table 2.
Example 2
Following example illustrates method provided by the invention.
Method by example 1 is carried out hydrofining to same stock oil, the condition that different is contacts with hydrogen with catalyzer after the virgin kerosene that contains dithiocarbonic anhydride 2 heavy % contacts is 350 ℃ of temperature, hydrogen flowing quantity is per hour 1200 milliliters of every gram catalyzer, 10 hours duration of contact, the results are shown in the table 2.
Example 3
This example illustrates method provided by the invention.
Method by example 1 is carried out hydrofining to same stock oil, different is contacts with the gas mixture of nitrogen with the hydrogen of a kind of hydrogen 90 body % with catalyzer after the virgin kerosene that contains dithiocarbonic anhydride 2 heavy % contacts, the flow of gas mixture is per hour 500 milliliters of every gram catalyzer (containing per hour 450 milliliters hydrogen of every gram catalyzer), the sulfuration rear catalyst is 370 ℃ with the temperature that contacts of the gas mixture of hydrogen, 24 hours duration of contact, the results are shown in Table 2.
Table 1
| The stock oil title | Catalytic diesel oil | Virgin kerosene |
| Density (20 ℃), g/cm 3 | 0.8956 | 0.7939 |
| Nitrogen content, ppm | 916 | 20 |
| Sulphur content, ppm | 5200 | 580 |
| Gum level, mg/100ml | 163 | ＜2 |
| Boiling range, ℃ initial boiling point 10% 50% 90% | 198 225 276 332 | 150 168 185 207 |
Table 2
| Example number | Denitrification percent, heavy % | Desulfurization degree, heavy % | Carbon deposit content, heavy % |
| 1 | 53.87 | 89.42 | 2.1 |
| Comparative Examples 1 | 45.36 | 86.52 | 4.8 |
| 2 | 54.06 | 90.03 | 3.0 |
| 3 | 52.14 | 89.73 | 1.8 |
Example 4
Following example illustrates method provided by the invention.
Press CN1,056, example 14 preparation catalyzer among the 514A, the nickel oxide 4.0 that consists of of catalyzer weighs %, Tungsten oxide 99.999 17.5 heavy %, fluorine 0.5 heavy %, surplus is the carrier that contains y-type zeolite.It is the bar of 1-2 millimeter that the catalyst breakage that obtains is become length, 300 milliliters of catalyzer after the fragmentation are packed in the reactor of medium-sized trickle bed reaction unit, feeding contains the straight-run diesel oil (character of straight-run diesel oil sees Table 3) of dithiocarbonic anhydride 2 heavy %, 300 ℃ of temperature, hydrogen dividing potential drop 6.0 MPas, liquid hourly space velocity 3.0 hours
-1, hydrogen to oil volume ratio is under 400 the condition, the described straight-run diesel oil that contains dithiocarbonic anhydride 2 heavy % to be contacted 36 hours with catalyzer.Then, stop to enter the virgin kerosene that contains dithiocarbonic anhydride, at 350 ℃, with flow be every gram catalyzer per hour 200 milliliters hydrogen contact 48 hours, then, introduce the vacuum gas oil shown in the table 3, reaction conditions is 360 ℃ of temperature of reaction, hydrogen dividing potential drop 6.0 MPas, liquid hourly space velocity 1.5 hours
-1, hydrogen to oil volume ratio 800.The reaction operation was stopped work after 500 hours, pressed the carbon deposit content that example 1 described method is surveyed catalyzer, the sulphur nitrogen content in the product oil, and the results are shown in Table 4.
Comparative Examples 2
Method by example 4 is carried out hydrotreatment to same stock oil, different directly introduces vacuum gas oil just with after the straight-run diesel oil that contains dithiocarbonic anhydride 2 heavy % contacts, and is as shown in table 4 without the process result that described catalyzer contacts with hydrogen.
Table 3
* do
| The stock oil title | Vacuum gas oil | Straight-run diesel oil |
| Density (20 ℃), g/cm 3 | 0.8803 | 0.8462 |
| Nitrogen content, ppm | 1290 | 72 |
| Sulphur content, heavy % | 0.43 | 1.28 |
| Carbon residue content, heavy % | 0.05 | - |
| Aromaticity content, heavy % | 23.5 | 30.0 |
| Boiling range, ℃ (ASTM D86) initial boiling point 50% 90% | 316 425 477 | 235 293 366* |
Table 4
| Example number | Nitrogen content in the product oil, ppm | Sulphur content in the product oil, ppm | Carbon deposit content, heavy % |
| 4 | 11 | 117 | 7.5 |
| Comparative Examples 2 | 24 | 211 | 11.3 |
Claims (16)
1. the method for pre-sulphuration of a hydrogenation catalyst, it is characterized in that, this method comprises and will contact with a kind of gas of hydrogen with catalyzer after vulcanized oil contacts, the temperature that catalyzer described and after vulcanized oil contacts contacts with the gas of hydrogen is 230-450 ℃, at least 0.5 hour duration of contact, the flow of the gas of hydrogen is per hour at least 5 milliliters of hydrogen of every gram catalyzer.
2. method according to claim 1 is characterized in that, the gas of described hydrogen refers to pure hydrogen or the hydrogen of hydrogen content at least 80 body % and the gas mixture of rare gas element.
3. method according to claim 2 is characterized in that described rare gas element refers to nitrogen.
4. method according to claim 1, it is characterized in that, the temperature that catalyzer described and after vulcanized oil contacts contacts with the gas of hydrogen is 300-420 ℃, and be 5-50 hour duration of contact, and the flow of the gas of hydrogen is a per hour 100-3000 milliliter hydrogen of every gram catalyzer.
5. method according to claim 1, it is characterized in that, the temperature that the vulcanized oil of described Containing Sulfur agent contacts with the oxidation state hydrogenation catalyst is 230-350 ℃, the pressure of contact is the 0.1-15 MPa, at least 0.5 hour duration of contact, hydrogen to oil volume ratio is 50-2000, and liquid hourly space velocity is 0.5-10 hour
-1
6. method according to claim 5 is characterized in that, described contact temperature is 250-320 ℃, and contact pressure is the 1-12 MPa, and be 2-48 hour duration of contact, and hydrogen to oil volume ratio is 100-1000, and liquid hourly space velocity is 1-4 hour
-1
7. method according to claim 1 or 5 is characterized in that described vulcanized oil is selected from kerosene or solar oil.
8. method according to claim 1 or 5 is characterized in that described vulcanizing agent is selected from hydrogen sulfide, dithiocarbonic anhydride or dimethyl thioether.
9. method according to claim 1 is characterized in that, the content of described vulcanizing agent in vulcanized oil is the heavy % of 0.1-10.
10. method according to claim 9 is characterized in that, the content of described vulcanizing agent in vulcanized oil is the heavy % of 1-5.
11. method is characterized in that according to claim 1 or 5, described oxidation state hydrogenation catalyst is selected from a kind of hydrogenation catalyst that contains oxidation state molybdenum and/or tungsten and nickel and/or cobalt.
12. method according to claim 11; it is characterized in that described oxidation state hydrogenation catalyst is selected from the molybdenum that contains a kind of heat-resistant inorganic oxide carrier, oxidation state and/or Hydrobon catalyst, hydrotreating catalyst or the hydrogenation protecting agent of tungsten and nickel and/or cobalt.
13. method according to claim 11 is characterized in that, described oxidation state hydrogenation catalyst refers to contain the molybdenum of zeolite, heat-resistant inorganic oxide, oxidation state and/or the hydrotreating catalyst or the hydrocracking catalyst of tungsten and nickel and/or cobalt.
14., it is characterized in that described heat-resistant inorganic oxide refers to aluminum oxide and/or silicon oxide according to claim 12 or 13 described methods.
15. according to claim 12 or 13 described methods, it is characterized in that, also contain a kind of adjuvant component in the described catalyzer, described adjuvant component is selected from one or more in fluorine, magnesium, phosphorus, VB family element, VIIB family element, IB family element, IIB family element, tin, antimony, bismuth and the tellurium.
16. method according to claim 15 is characterized in that, described adjuvant component is selected from fluorine, magnesium or phosphorus.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100360236C (en) * | 2005-05-12 | 2008-01-09 | 中国石油化工股份有限公司 | Treatment method before application of hydrogenation catalyst |
| CN100413587C (en) * | 2005-05-12 | 2008-08-27 | 中国石油化工股份有限公司 | Sulfurized type catalyst, and its prepn. method |
| US8262905B2 (en) * | 2009-03-19 | 2012-09-11 | Shell Oil Company | Oil and polar additive impregnated composition useful in the catalytic hydroprocessing of hydrocarbons, a method of making such catalyst, and a process of using such catalyst |
| CN103059910B (en) * | 2011-10-21 | 2014-12-31 | 中国石油化工股份有限公司 | Vulcanization method of hydrofining catalyst |
| CN103100449B (en) * | 2011-11-10 | 2015-04-15 | 中国石油化工股份有限公司 | Startup sulfuration method of liquid phase circulation hydrogenation unit |
| CN102604664A (en) * | 2012-03-23 | 2012-07-25 | 海南朗洁新能源科技有限公司 | Method for producing high-cetane-number diesel oil on hydrogenation device by using triglyceride |
| CN105316030B (en) * | 2014-07-18 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of hydrodeoxygenation process |
| CN106140314B (en) * | 2015-04-15 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its application |
| CN106925356B (en) * | 2015-12-30 | 2020-06-09 | 中国石油天然气股份有限公司 | Pre-sulfurizing method of hydrogenation catalyst |
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