CN1351111A - Process for presulfurizing hydrocatalyst - Google Patents
Process for presulfurizing hydrocatalyst Download PDFInfo
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- CN1351111A CN1351111A CN 00129838 CN00129838A CN1351111A CN 1351111 A CN1351111 A CN 1351111A CN 00129838 CN00129838 CN 00129838 CN 00129838 A CN00129838 A CN 00129838A CN 1351111 A CN1351111 A CN 1351111A
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Abstract
A process for presulfurizing hydrocatalyst includes presulfurizing a hydrocatalyst in oxidation state, contacting with hydrocarbon oil under existance of hydrogen gas at 250-420 deg.C for 2-500 hr, and contacting with hydrogen-contained gas at 230-450 deg.C for at least 0.5 hr. It can obviously decrease the carbon deposit on hydrocatalyst and improve its activity stability.
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; To produce oil fuel is hydrocracking catalyst of purpose or the like.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 both 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, and to this, " Chinese oil Refining Technologies " waits sample unicorn chief editor, Sinopec press, and 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 is contacted with a kind of hydrotreating catalyst with hydrogen, 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, metal oxide-loaded catalyzer 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 organosulfur compound 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 catalyzer method that a kind of processing contains 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 organosulfur compound 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.
The method for pre-sulphuration of hydrogenation catalyst provided by the invention comprises with the outer prevulcanized method of gas phase prevulcanized method or device a kind of oxidation state hydrogenation catalyst is carried out prevulcanized, this method also is included under the hydrogen existence and will contacts with a kind of hydrocarbon ils with gas phase prevulcanized method or the outer prevulcanized method sulfurized catalyzer of device, and then contact with a kind of gas of hydrogen, the condition that described and a kind of hydrocarbon ils contacts is 250-420 ℃ for the contact temperature, contact pressure is the 0.1-15 MPa, hydrogen to oil volume ratio is 50-2000, and liquid hourly space velocity is 0.1-10 hour
-1, be 0.2-500 hour duration of contact; The described condition that contacts with the gas of hydrogen is at least 0.5 hour for the contact temperature is 230-450 ℃ 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, describedly be preferably with the outer prevulcanized method sulfurized catalyzer of gas phase prevulcanized method or device and the contact conditions of described hydrocarbon ils that to contact temperature be 300-400 ℃, contact pressure is 1-12 million, and hydrogen to oil volume ratio is 100-1500, and liquid hourly space velocity is 0.5-5 hour
-1, be 5-300 hour duration of contact.
Described hydrocarbon ils is selected from the various hydrocarbon ils that can be used as the hydrogenation reaction raw material, as straight-run spirit, kerosene, diesel oil, atmosphere 3rd side cut distillate, second line of distillation distillate, subtract in three-way distillate, vacuum gas oil, catalytic cracking diesel oil and the coker gas oil one or more.Be preferably virgin kerosene, diesel oil or atmosphere 3rd side cut distillate or the mixture of 2 kinds or 3 kinds in them.
The described condition optimization that contacts with the gas of hydrogen is 300-420 ℃ for the contact temperature, and be 1-50 hour duration of contact, more preferably 5-50 hour.The flow of the gas of hydrogen can be very big, is preferably every gram catalyzer per minute 100-3000 milliliter hydrogen.The pressure of contact does not have special requirement.
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.
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, described group vib hydrogenation active metals is preferably molybdenum and/or tungsten, and 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 hydrotreating catalyst 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, described zeolite is selected from one or more in mesopore and the large pore zeolite, 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.
Described gas phase prevulcanized method refers to existing various gas phase prevulcanized method, the process of described gas phase prevulcanized method, vulcanizing agent, cure conditions have been conventionally known to one of skill in the art, for example " Chinese oil Refining Technologies ", the Hou Xianglin chief editor, Sinopec press, P279-281,1991 pairs of gas phase prevulcanized methods commonly used are explained in detail.
According to embodiment preferred of the present invention, described gas phase prevulcanized method comprises a kind of hydrogen that contains the gaseous state vulcanizing agent is contacted with described oxidation state hydrogenation catalyst, the contact temperature is 170-500 ℃, be preferably 300-500 ℃, contact pressure is the 0.1-12 MPa, be preferably the 1-8 MPa, be 10-60 hour duration of contact, be preferably 20-60 hour, the content of vulcanizing agent in hydrogen is 0.1-5 body %, preferred 0.3-4 body %, the flow of the hydrogen of Containing Sulfur agent is a per hour 100-2000 milliliter of every gram catalyzer, is preferably per hour 200-1500 of every gram catalyzer.Described vulcanizing agent can be selected from hydrogen sulfide or dithiocarbonic anhydride.
The outer prevulcanized method of described device refers to the outer method for pre-sulphuration of existing various device, as US4,089,930 disclosed be the outer method for pre-sulphuration of device of vulcanizing agent with the elementary sulfur, EP359,356A1 is disclosed to be the outer method for pre-sulphuration of device of vulcanizing agent with the elementary sulfur, US5,215,954 disclosed be the outer method for pre-sulphuration of device of vulcanizing agent with the elementary sulfur, US5,139,990 disclosed be the method for vulcanizing agent with the organosulfur compound, US5,681,787 disclosed be the outer method for pre-sulphuration of device of vulcanizing agent with the elementary sulfur, CN85,107,953A is disclosed to be the method for vulcanizing agent with the organic polysulfide, CN1,082,591A is disclosed to be outer method for pre-sulphuration of device of vulcanizing agent or the like with organic sulfide and/or elementary sulfur.Only listed the outer method for pre-sulphuration of existing part device above, be not construed as limiting the invention, in method provided by the invention, catalyzer is being contacted with described hydrocarbon ils and, can adopt any existing gas phase prevulcanized method or device prevulcanized method outward with before the gas of hydrogen contacts.
Adopt method provided by the invention that hydrogenation catalyst is carried out the coke content that prevulcanized can obviously reduce hydrogenation catalyst in the hydrogenation process, the stability of catalyzer is significantly improved.For example, after according to method provided by the invention the Hydrobon catalyst that contains nickel oxide 2.0 heavy %, tungsten fluoride 21.2 heavy %, fluorine 4.4 heavy % and surplus alumina supporter being carried out prevulcanized, 350 ℃, 3.2 MPas, hydrogen to oil volume ratio is 500, liquid hourly space velocity is 2.0 hours
-1Situation under the catalytic diesel oil of nitrogenous 916ppm, sulphur 5200ppm is carried out hydrofining, react after 300 hours, carbon deposit content has only 3.5 heavy % on the catalyzer, denitrification percent reaches 52.53 heavy %, and desulfurization degree reaches 88.10 heavy %, and adopts traditional method for pre-sulphuration, other condition and catalyzer homogeneous phase are simultaneously, carbon deposit content is up to 5.2 heavy % on the catalyzer, and desulfurization degree has only 47.32 heavy %, and denitrification percent has only 86.34 heavy %.
The following examples will the present invention will be further described.
Example 1
This example illustrates method for pre-sulphuration provided by the invention.
Press CN85,104, the method for 438B example 3 prepares Hydrobon catalyst, and 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, 100 milliliters of catalyzer after the fragmentation are packed in the reactor of medium-sized trickle bed reaction unit, feed the hydrogen of sulfide hydrogen 0.2 body %, the pressure of sulfide hydrogen hydrogen is 3.2 MPas, the flow of sulfide hydrogen hydrogen is per hour 1000 milliliters of every gram catalyzer, be warming up to 480 ℃, constant temperature 24 hours obtains with gas phase prevulcanized method sulfurized catalyzer.Then, at the catalytic diesel oil shown in 330 ℃ of following switching tables 1, at 3.2 MPa pressure, under 2 hours-1 the condition of hydrogen to oil volume ratio 400 and liquid hourly space velocity, with described catalytic diesel oil with the sulfuration after catalyzer contact 10 hours, cut off catalytic diesel oil, adjusting hydrogen flowing quantity is per hour 200 milliliters hydrogen (hydrogen 99.9 body %) of every gram catalyzer, under 330 ℃ temperature, hydrogen is contacted 12 hours with catalyzer, and then feed catalytic diesel oil shown in the table 1, and described catalytic diesel oil is carried out hydrofining, purification condition is 350 ℃ of temperature of reaction, hydrogen dividing potential drop 3.2 MPas, liquid hourly space velocity 2.0 hours
-1, hydrogen to oil volume ratio is 500.Reaction is carried out stopping work after 300 hours, the sulphur of analysed preparation oil, nitrogen content, and calculate denitrification percent and desulfurization degree, the results list is in 2.Catalyzer being taken out from reactor, get 20 gram samples, is that solvent carries out cable-styled 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 the sh/T0253-92 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
By example 1 method same catalyzer is carried out prevulcanized and same stock oil is carried out hydrofining, different hydrogen sulfide containing hydrogen and the constant temperature of just feeding are after 24 hours, directly switch stock oil, under identical purification condition, stock oil is made with extra care, without the process that contacts with hydrogen, reaction times is 280 hours, and the results are shown in Table 2.
Example 2
This example illustrates method for pre-sulphuration provided by the invention.
Method by example 1 is carried out prevulcanized and same raw material is carried out hydrofining same catalyzer, different is, with hydrogen sulfide containing hydrogen duration of contact be 48 hours, described catalyzer with the contact conditions of catalytic diesel oil is: contact 350 ℃ of temperature, contact pressure is 8.0 MPas, hydrogen to oil volume ratio is 800, liquid hourly space velocity 3.0 hours
-1, be 24 hours duration of contact; Describedly with the contact conditions of hydrogen be: contact 370 ℃ of temperature, 12 hours duration of contact, hydrogen flowing quantity is per hour 1000 milliliters of every gram catalyzer, and the results are shown in Table 2.
Example 3
This example illustrates method for pre-sulphuration provided by the invention.
Method by example 1 is carried out prevulcanized and same stock oil is carried out hydrofining same catalyzer, different is, after hydrogen sulfide containing hydrogen contacted 24 hours, catalyzer is contacted with the virgin kerosene shown in the table 1, the contact temperature is 300 ℃, contact pressure is 2.0 MPas, and hydrogen to oil volume ratio is 200, liquid hourly space velocity 3.5 hours
-1, be 200 hours duration of contact; Then, contact with the hydrogen of a kind of hydrogen 90 body % and the gas mixture of nitrogen, the contact temperature is 320 ℃, and be 36 hours duration of contact, and mixed gas flow is per hour 150 milliliters of every gram catalyzer (closing 135 milliliters of hydrogen of every gram catalyzer per minute).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 | ????52.53 | ????88.10 | ????3.5 |
| Comparative Examples 1 | ????47.32 | ????86.34 | ????5.2 |
| ????2 | ????54.31 | ????89.64 | ????3.0 |
| ????3 | ????52.11 | ????87.69 | ????3.2 |
Example 4-5
This 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, carries out prevulcanized respectively as follows:
Method 1, in the reactor with 100 milliliters of the catalyzer after the fragmentation (being equivalent to 86 grams) the medium-sized trickle bed reaction unit of packing into, feed the hydrogen of sulfide hydrogen 2.5 body %, the pressure of sulfide hydrogen hydrogen is 8 MPas, and flow is per hour 1000 milliliters of every gram catalyzer, is warming up to 480 ℃, constant temperature 48 hours, then, the vacuum gas oil shown in the switching table 3 under 370 ℃ temperature was 8.0 MPa pressure, hydrogen to oil volume ratio 800 and liquid hourly space velocity 1.0 hours
-1Condition under, described vacuum gas oil is contacted 24 hours with catalyzer, cut off vacuum gas oil, adjusting hydrogen flowing quantity is per hour 500 milliliters hydrogen (specification is with example 1) of every gram catalyzer, 370 ℃ temperature, described hydrogen is contacted 24 hours with catalyzer.
Method 2 is pressed US4, and 177,136 examples, 1 method is carried out the outer prevulcanized of device to catalyzer.86 gram catalyzer (pore volume be 0.43 milliliter/gram) being placed in the tubular reactor, add sulphur simple substance 10 grams above catalyzer, is that every gram catalyzer per hour is warming up to 120 ℃ under 1000 milliliters the nitrogen gas stream at flow, is cooled to room temperature after about 30 minutes.In the reactor with 100 milliliters of medium-sized trickle bed reaction units of packing into of the catalyzer that contains elementary sulfur of obtaining, be 371 ℃ in temperature, pressure is 8.0 MPas, hydrogen to oil volume ratio be 800 and liquid hourly space velocity be 1.0 hours
-1Condition under, vacuum gas oil shown in the table 3 is contacted 24 hours with catalyzer, cut off vacuum gas oil, the flow of adjusting hydrogen is per hour 200 milliliters a hydrogen (specification is with example 1) of every gram catalyzer, under 370 ℃ temperature, described hydrogen is contacted 24 hours with catalyzer.
Vacuum gas oil shown in the feeding table 3 and hydrogen respectively in the reactor that the catalyzer that carries out prevulcanized with method 1 or method 2 is housed, all 370 ℃ of temperature of reaction, reaction pressure 8.0 MPas, hydrogen to oil volume ratio is 800, liquid hourly space velocity is 1.0 hours
-1Condition under, described vacuum gas oil is carried out hydrotreatment, turn round after 500 hours and to stop work, measure sulphur, nitrogen content in the product respectively, the results are shown in Table 4.Catalyzer being taken out from reactor respectively, get 20 gram samples respectively, is that solvent carries out the Soxhlet extracting with toluene, and the carbon deposit content in the catalyzer is measured in oven dry respectively, and the results are shown in Table 4.
Comparative Examples 2
With the method identical catalyzer is carried out prevulcanized and same stock oil is carried out hydrofining with example 4, different is, feed hydrogen sulfide containing gas and constant temperature after 24 hours, directly switch stock oil, under identical purification condition, directly stock oil is carried out hydrofining, and do not have the contact process of catalyzer and hydrogen, the results are shown in Table 4.
Comparative Examples 3
With the method identical catalyzer is carried out prevulcanized with example 5, and same stock oil carried out hydrofining, different is directly under identical purification condition identical stock oil to be carried out hydrofining with the catalyzer that contains elementary sulfur, and do not have the contact process of catalyzer and hydrogen, the results are shown in Table 4.
Table 3
| The stock oil title | Vacuum gas oil |
| Density (20 ℃), g/cm 3 | ????0.8803 |
| Nitrogen content, ppm | ????1290 |
| Sulphur content, ppm | ????4300 |
| Carbon residue content, heavy % | ????0.05 |
| Aromaticity content, heavy % | ????23.5 |
| Boiling range, ℃ (ASTM D86) initial boiling point 10% 50% 90% | ????316 ????372 ????425 ????477 |
Table 4
| Example number | Nitrogen content in the product oil, ppm | Sulphur content in the product oil, ppm | Carbon deposit content, heavy % |
| Example 4 | ????3.2 | ????5.6 | ????9.3 |
| Comparative Examples 2 | ????6.4 | ????11.3 | ????13.1 |
| Example 5 | ????＜1 | ????4.5 | ????10.2 |
| Comparative Examples 3 | ????10.2 | ????9.8 | ????14.5 |
Claims (16)
1. the method for pre-sulphuration of a hydrogenation catalyst comprises with the outer prevulcanized method of gas phase prevulcanized method or device a kind of oxidation state hydrogenation catalyst is carried out prevulcanized, it is characterized in that, this method also is included in hydrogen and exists down, to contact with a kind of hydrocarbon ils with gas phase prevulcanized method or the outer prevulcanized method sulfurized catalyzer of device, then, contact with a kind of gas of hydrogen again, the described condition that contacts with hydrocarbon ils is 250-420 ℃ for the contact temperature, contact pressure is the 0.1-15 MPa, hydrogen to oil volume ratio is 50-2000, and liquid hourly space velocity is 0.1-10 hour
-1, be 2-500 hour duration of contact; The described condition that contacts with the gas of hydrogen is at least 0.5 hour for the contact temperature is 230-450 ℃ duration of contact, and 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 described condition that contacts with hydrocarbon ils is 300-400 ℃ for the contact temperature, and contact pressure is the 1-12 MPa, and hydrogen to oil volume ratio is 100-1500, and liquid hourly space velocity is 0.5-5 hour
-1, be 5-300 hour duration of contact.
3. method according to claim 1 and 2 is characterized in that, described hydrocarbon ils is selected from straight-run spirit, kerosene, diesel oil, atmosphere 3rd side cut distillate, second line of distillation distillate, subtract in three-way distillate, catalytic cracking diesel oil and the coker gas oil one or more.
4. method according to claim 3 is characterized in that, described hydrocarbon ils is selected from virgin kerosene, diesel oil or atmosphere 3rd side cut distillate or the mixing oil of 2 kinds or 3 kinds in them.
5. method according to claim 1, it is characterized in that, the described condition that contacts with the gas of hydrogen is 300-420 ℃ for the contact temperature, 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.
6. method according to claim 1 or 5 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.
7. method according to claim 6 is characterized in that described rare gas element refers to nitrogen.
8. method according to claim 1 is characterized in that, described oxidation state hydrogenation catalyst is selected from a kind of molybdenum of oxidation state and/or hydrogenation catalyst of tungsten and nickel and/or cobalt of containing.
9. method according to claim 8; 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.
10. method according to claim 8 is characterized in that, described oxidation state hydrogenation catalyst is selected from the molybdenum that contains zeolite, heat-resistant inorganic oxide, oxidation state and/or the hydrotreating catalyst or the hydrocracking catalyst of tungsten and nickel and/or cobalt.
11., it is characterized in that described heat-resistant inorganic oxide refers to aluminum oxide and/or silicon oxide according to claim 9 or 10 described methods.
12. according to claim 9 or 10 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.
13. method according to claim 12 is characterized in that, described adjuvant component is selected from fluorine, magnesium or phosphorus.
14. method according to claim 1, it is characterized in that, described gas phase prevulcanized comprises a kind of hydrogen that contains the gaseous state vulcanizing agent is contacted with described oxidation state hydrogenation catalyst, the temperature of contact is 170-500 ℃, the pressure of contact is the 0.1-12 MPa, the time of contact is 10-60 hour, and the content of vulcanizing agent in hydrogen is 0.1-5 body %, and the flow of the hydrogen of Containing Sulfur agent is a per hour 100-2000 milliliter of every gram catalyzer.
15. method according to claim 14, it is characterized in that, described contact temperature is 300-500 ℃, the pressure of contact is the 1-8 MPa, be 20-60 hour duration of contact, the content of vulcanizing agent in hydrogen is 0.2-4 body %, and the flow of the hydrogen of Containing Sulfur agent is per hour 200-1500 of every gram catalyzer.
16., it is characterized in that described vulcanizing agent is hydrogen sulfide, dithiocarbonic anhydride according to claim 14 or 15 described methods.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448542C (en) * | 2004-10-29 | 2009-01-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst precuring method |
| CN103100449A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Startup sulfuration method of liquid phase circulation hydrogenation unit |
| CN105521791A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for preparing sulfuration-type gasoline selective hydro-desulfurization catalyst |
| CN105586073A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Pre-sulfurization method for gasoline selective hydrodesulfurization catalyst |
| CN105586072A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Pre-sulfuration method for hydrodesulfurization catalyst |
| CN106669788A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN110479312A (en) * | 2018-05-15 | 2019-11-22 | 中国石油化工股份有限公司 | Hydrogenation catalyst and its preparation method and application and the method for hydrofinishing |
| CN111068795A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | External presulfurization method of hydrogenation catalyst |
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2000
- 2000-10-30 CN CN 00129838 patent/CN1115385C/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448542C (en) * | 2004-10-29 | 2009-01-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst precuring method |
| CN103100449A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Startup sulfuration method of liquid phase circulation hydrogenation unit |
| 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 |
| CN105586073B (en) * | 2014-10-22 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of catalyst for selective hydrodesulfurizationof of gasoline method for pre-sulphuration |
| CN105586073A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Pre-sulfurization method for gasoline selective hydrodesulfurization catalyst |
| CN105586072A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Pre-sulfuration method for hydrodesulfurization catalyst |
| CN105586072B (en) * | 2014-10-22 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst method for pre-sulphuration |
| CN105521791B (en) * | 2014-10-22 | 2017-10-27 | 中国石油化工股份有限公司 | The preparation method of vulcanization type catalyst for selective hydrodesulfurizationof of gasoline |
| CN105521791A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for preparing sulfuration-type gasoline selective hydro-desulfurization catalyst |
| CN106669788A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN106669788B (en) * | 2015-11-11 | 2019-07-12 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN110479312A (en) * | 2018-05-15 | 2019-11-22 | 中国石油化工股份有限公司 | Hydrogenation catalyst and its preparation method and application and the method for hydrofinishing |
| CN110479312B (en) * | 2018-05-15 | 2022-03-11 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof, and hydrofining method |
| CN111068795A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | External presulfurization method of hydrogenation catalyst |
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