CN1417299A - Pre-sulfurizing process of hydrogenating catalyst - Google Patents
Pre-sulfurizing process of hydrogenating catalyst Download PDFInfo
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Abstract
The pre-sulfurizing process of hydrogenating catalyst includes impregnating the hydrogenating catalyst in solution containing sulfurized olefin at room temp-220 deg.c for 0.5-5 hr, and heating catalyst in inert atmosphere. The solution containing sulfurizing olefin is in the temperature of room temperature to 220 deg.c and has dissolved S element, total S content of 4-40 wt% and the weight ratio between S in element state and S in sulfurized olefin of 0.5-7. The sulfurized hydrogenating catalyst contains S in 1-7.5 w. The pre-sulfurizing process of hydrogenating catalyst can lower its breaking rate greatly and raise the S retention degree.
Description
Technical field
The invention relates to a kind of method for pre-sulphuration of hydrogenation catalyst.
Background technology
CN1262305A discloses a kind of method for pre-sulphuration of hydrogenation catalyst, this method comprises the 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, this method comprises that also (1) mix a kind of component that contains alkene, elementary sulfur and auxiliary agent, at the 100-220 ℃ of described mixture of heating more than 0.5 hour.Wherein the mole number of elementary sulfur is no less than the mole number of olefinic double bonds, and the consumption of auxiliary agent is the heavy % of the 10-80 of elementary sulfur consumption, and described auxiliary agent is selected from one or more in the used organic additive of the vulcanization of rubber; (2) product of the Containing Sulfur alkene that (1) is obtained dipping is introduced the catalyzer of elementary sulfur, and under inert atmosphere in 100-300 ℃ of heatable catalyst more than 1 hour, wherein, the volumetric usage of the product of Containing Sulfur alkene is at least 60% of catalyst pore volume.
This method has overcome in the past the outer method for pre-sulphuration of device and has used the higher shortcoming of organic polysulfide cost, and, improved the reservation degree of sulphur.Yet, this method is with to use elementary sulfur the same as the method for pre-sulphuration of vulcanizing agent in the past, owing to use elementary sulfur as vulcanizing agent, macroelement sulphur concentrates in the duct of catalyzer, in the prevulcanized and use of catalyzer, catalyzer all need pass through heat treatment process, elementary sulfur in heat treatment process in the catalyzer duct is met heat volumetric expansion is taken place, make the granules of catalyst fragmentation easily, thereby, making the catalyzer after the sulfuration have higher percentage of damage, also is like this in the catalyzer use.Moreover this method adopts earlier and to be dipped in the catalyzer elementary sulfur is dried, uses the product impregnated catalyst of Containing Sulfur alkene again, the method for heatable catalyst then, and step is comparatively cumbersome.
Summary of the invention
It is higher to the objective of the invention is to overcome existing hydrogenation catalyst presulfurizing method percentage of damage, and the shortcoming that step is complicated provides a kind of simpler, and the method for pre-sulphuration of the lower hydrogenation catalyst of the hydrogenation catalyst percentage of damage after the sulfuration.
As previously mentioned, according to the method for CN1262305A, with the solution impregnation catalyst of Containing Sulfur alkene, though can introduce part sulphur.But on the one hand, the sulphur content of olefine sulfide is lower, and when the hydrogenation active metals content in the catalyzer was higher, only the solution of using Containing Sulfur alkene can not be introduced the sulphur of q.s as vulcanizing agent in catalyzer.On the other hand, result of study shows, when containing elementary sulfur in the vulcanizing agent, sulphur in the catalyzer after the prevulcanized forms a kind of crosslinked sulphur compound, it is a kind of cancellated sulphur compound, the thiopectic effect of this crosslinked sulphur compound is very strong, therefore, catalyzer after the prevulcanized has higher sulphur reservation degree, if and do not contain elementary sulfur in the vulcanizing agent, just during olefine sulfide, then can not form this crosslinked sulphur compound, just with olefine sulfide as vulcanizing agent and non-added elements sulphur, the sulphur reservation degree of the catalyzer after the prevulcanized reduces greatly.Therefore, also must spoke to introduce solid state elements sulphur with the dried method of soaking of elementary sulfur, so just cause the percentage of damage that vulcanizes the back end hydrogenation catalyzer higher inevitably.The present inventor finds in experiment, olefine sulfide can dissolve a certain amount of sulphur at normal temperatures, can dissolve more elementary sulfur in that higher temperature is next, simultaneously, when solvent temperature is 100-220 ℃, its product is dissolved with promptly that total sulfur content is lower than at 28% o'clock in the solution of Containing Sulfur alkene of elementary sulfur, even temperature is reduced to room temperature, the sulphur that is dissolved in is wherein also no longer separated out.Yet, at room temperature, when the content of sulphur is not less than 18 weight %, be dissolved with the very thickness of the olefine sulfide change of elementary sulfur, can not be used as steeping fluid.According to this phenomenon, the present inventor has invented a kind of method for pre-sulphuration of new hydrogenation catalyst, and this method does not re-use elementary sulfur, and the solution that directly uses the Containing Sulfur alkene that is dissolved with elementary sulfur is as steeping fluid.Adopt this method, not only saved dried step and corresponding apparatus of soaking solid element sulphur, and the percentage of damage of the hydrogenation catalyst after the sulfuration is reduced significantly.
The method for pre-sulphuration of hydrogenation catalyst provided by the invention comprises with a kind of hydrogenation catalyst of a kind of solution impregnation of Containing Sulfur alkene, under inert atmosphere, heat this catalyzer then, wherein, the solution of described Containing Sulfur alkene is that temperature is a room temperature to 220 ℃, be dissolved with the solution of the Containing Sulfur alkene of elementary sulfur, total amount with solution is a benchmark, in elementary sulfur, the total content that is dissolved with sulphur in the solution of Containing Sulfur alkene of elementary sulfur is the heavy % of 4-40, wherein, the sulphur that exists with elementary state is 0.5-7 with the weight ratio of the sulphur that exists with olefine sulfide, and the temperature of dipping is a room temperature to 220 ℃; With the hydrogenation catalyst after the sulfuration is benchmark, and in elementary sulfur, the consumption of the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur makes the sulphur that contains the heavy % of 1-7.5 in the hydrogenation catalyst after the sulfuration.
The method for pre-sulphuration of hydrogenation catalyst provided by the invention has following advantage:
1. adopt method provided by the invention that hydrogenation catalyst is carried out prevulcanized, the percentage of damage of the hydrogenation catalyst after the sulfuration reduces significantly.For example, adopt method provided by the invention, the solution of the Containing Sulfur alkene that is dissolved with elementary sulfur that with temperature is 140 ℃ sulfur-bearing 26.3 heavy % floods a kind of nickel oxide 2.5 heavy % that contain under 140 ℃ of temperature, the hydrotreating catalyst of Tungsten oxide 99.999 26.4 heavy %, and under 205 ℃ nitrogen atmosphere, heated 3 hours, the percentage of damage of the catalyzer after the sulfuration that obtains has only 0.3%, and the method for employing CN1262305A, to the same dried elementary sulfur that soaks of catalyzer elder generation, use the olefine sulfide impregnated catalyst again, then the same time of heating under same temperature and atmosphere, the percentage of damage of the catalyzer after the sulfuration that obtains is up to 3.0 heavy %.Compared with prior art, use method provided by the invention, the percentage of damage of sulfuration rear catalyst has descended 90%.
2. hydrogenation catalyst provided by the invention has saved dried step and the equipment that soaks sulphur, and is therefore not only more simple, and reduced cost.
3. adopt method provided by the invention that hydrogenation catalyst is carried out prevulcanized, the sulphur of the catalyzer after the sulfuration keeps Du Genggao.For example, adopt method provided by the invention, with temperature is the solution of 140 ℃ the sulfur-bearing 26.3% Containing Sulfur alkene that is dissolved with elementary sulfur heavily, the aforesaid hydrotreating catalyst of dipping under 140 ℃ temperature, and under 205 ℃ nitrogen atmosphere, heated 3 hours, catalyzer after obtaining vulcanizing, the sulphur reservation degree of measuring the sulfuration rear catalyst with the acetone extraction test is 91.3 heavy %, and the method for employing CN1262305A, to same catalyzer, the dried elementary sulfur that soaks of elder generation, use the solution impregnation catalyst of the Containing Sulfur alkene that does not contain elementary sulfur again, then, the same time of heating under same temperature and atmosphere, the sulphur reservation degree of sulfuration rear catalyst has only 89.1 heavy %.
Embodiment
According to method provided by the invention, total amount with solution is a benchmark, in elementary sulfur, the total content of sulphur is the heavy % of 4-40 in the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur, be preferably the heavy % of 10-35, described weight ratio with elementary state sulphur that exists and the sulphur that exists with olefine sulfide is 0.5-7, is preferably 1-5.
According to method provided by the invention, when the hydrogenation metal content in the described catalyzer is higher, need solution with the higher Containing Sulfur alkene that is dissolved with elementary sulfur of concentration, promptly total sulfur content is not less than the solution of the Containing Sulfur alkene that is dissolved with elementary sulfur of 18 heavy %.When the hydrogenation metal content in the described catalyzer is low, need solution with the lower Containing Sulfur alkene that is dissolved with elementary sulfur of concentration, promptly total sulfur content is lower than the solution of the Containing Sulfur alkene that is dissolved with elementary sulfur of 18 heavy %.The solution of the Containing Sulfur alkene that is dissolved with elementary sulfur that concentration is lower, it is the solution described catalyzer of direct impregnation at room temperature of the total sulfur content Containing Sulfur alkene that is lower than 18 heavy %, also can be in higher temperature, as be higher than under the temperature of room temperature to 200 ℃ catalyzer as described in the dipping, the temperature that is described solution can be a room temperature to 200 ℃, and the temperature of described dipping can be a room temperature to 200 ℃.And the solution of the higher Containing Sulfur alkene that is dissolved with elementary sulfur of concentration, be that the solution that total sulfur content is not less than the Containing Sulfur alkene that is dissolved with elementary sulfur of 18 heavy % at room temperature are a kind of very heavy-gravity solution, can't directly be used as steeping fluid, therefore, when the sulphur content in the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur is not less than 18 heavy %, the temperature of described solution is 100-200 ℃, be preferably 100-160 ℃, the temperature of described dipping is 100-200 ℃, is preferably 100-160 ℃.Because major part is the higher catalyzer of metal content in the existing hydrogenation catalyst, therefore, selecting temperature for use is 100-200 ℃, be preferably 100-160 ℃, total sulfur content is not less than the solution of the Containing Sulfur alkene that is dissolved with elementary sulfur of 18 heavy % and 100-200 ℃, the dipping temperature that is preferably 100-160 ℃ has prior meaning, also is the part place of the marrow of the present invention.
Difference according to hydrogenation metal content in the hydrogenation catalyst, should contain in the hydrogenation catalyst after the sulfuration, in element, the heavy % of 1-7.5, the sulphur of the heavy % of preferred 3-6.5, therefore, the consumption of the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur should make in the hydrogenation catalyst after the sulfuration and contain, and is benchmark with the hydrogenation catalyst after the sulfuration, in elementary sulfur, 1-7.5 heavy %, the sulphur of the heavy % of preferred 3-6.5.
Wherein, the solution of described Containing Sulfur alkene can be a kind of bright sulfur alkene, as vulcanize in monoene, diene or the polyenoid one or more, and also can be that olefine sulfide content is not less than 30 heavy %, preferably be not less than the varsol of 40 heavy % and the mixing solutions of olefine sulfide.Described olefine sulfide can be sulfurized straight chain, side chain or cyclic olefin, be preferably the olefine sulfide that contains 5-30 carbon atom, described varsol be included under the described immersion condition for liquid and with the miscible hydro carbons of olefine sulfide in one or more, as in liquid alkane, naphthenic hydrocarbon, the aromatic hydrocarbons one or more.
The solution of described Containing Sulfur alkene can be purchased and get, and also can directly mix with elementary sulfur under 100-220 ℃ temperature, and elementary sulfur and a kind of raw material reaction 0.5-5 hour of containing alkene are obtained.Under the preferable case, the method for employing CN1262305A prepares the solution of Containing Sulfur alkene.
The preparation method of the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur is as follows: the solution of elementary sulfur with a kind of Containing Sulfur alkene is mixed, at 100-220 ℃, heat under preferred 100-160 ℃ the temperature, dissolve fully until elementary sulfur.
According to specific embodiment of the present invention, the described solution that is dissolved with the Containing Sulfur alkene of elementary sulfur is prepared as follows: (1) mixes a kind of component and elementary sulfur that contains alkene, at 100-220 ℃, be preferably 130-210 ℃, more preferably heated described mixture 0.5-10 hour under 150-190 ℃ the temperature, preferred 0.5-5 hour, wherein, the mol ratio of elementary sulfur and olefinic double bonds is 1-1.5, the cooling or not cooled product to room temperature, the product liquid that obtains is the solution of Containing Sulfur alkene, (2) solution with the Containing Sulfur alkene that obtains mixes with elementary sulfur, at 100-220 ℃, heat under preferred 140-200 ℃ the temperature, elementary sulfur is dissolved fully, obtain being dissolved with the solution of the Containing Sulfur alkene of elementary sulfur, the heating for dissolving time was generally 0.1-2 hour, preferred 0.5-1.0 hour, the consumption of the solution of elementary sulfur and Containing Sulfur alkene makes the total content of sulphur in the solution of the Containing Sulfur alkene that finally is dissolved with elementary sulfur be, in elementary sulfur, the heavy % of 4-40, being preferably the sulphur of the heavy % of 10-35, is 0.5-7 with the weight ratio of elementary state sulphur that exists and the sulphur that exists with olefine sulfide, is preferably 1-5.
According to another specific embodiment of the present invention, the described solution that is dissolved with the Containing Sulfur alkene of elementary sulfur is prepared as follows: (1) is with a kind of component that contains alkene, elementary sulfur and auxiliary agent mix, at 100-220 ℃, be preferably 130-210 ℃, more preferably heated described mixture 0.5-10 hour under 150-190 ℃ the temperature, preferred 0.5-5 hour, wherein, the mol ratio of elementary sulfur and olefinic double bonds is 1-1.5, when described auxiliary agent is selected from the vulcanization of rubber in the used organic additive one or more, auxiliary dosage be the elementary sulfur consumption greater than to 80 heavy %, be preferably the heavy % of 10-50, the cooling or not cooled product to room temperature, the product liquid that obtains is the solution of Containing Sulfur alkene, (2) solution with the Containing Sulfur alkene that obtains mixes with elementary sulfur, at 100-220 ℃, heat under preferred 140-200 ℃ the temperature, elementary sulfur is dissolved fully, the time of heating for dissolving was generally 0.1-2 hour, preferred 0.5-1.0 hour, obtain being dissolved with the solution of the Containing Sulfur alkene of elementary sulfur, the consumption of the solution of elementary sulfur and Containing Sulfur alkene, make the total content of sulphur in the solution of the Containing Sulfur alkene that finally is dissolved with elementary sulfur be, in elementary sulfur, the heavy % of 4-40 is preferably the sulphur that 10-35 weighs %, weight ratio with elementary state sulphur that exists and the sulphur that exists with olefine sulfide is 0.5-7, is preferably 1-5.
The described component that contains alkene can be one or more in pure liquid monoene, diene and the polyenoid, and described monoene, diene and polyenoid can be straight chain, side chain or cyclic olefin.Described alkene preferably contains the alkene of 5-30 carbon atom.Can contain other hydrocarbon components in the described component that contains alkene, as in alkane, naphthenic hydrocarbon, the aromatic hydrocarbons one or more, olefin(e) centent is the heavy % of 30-100 in the described component that contains alkene.For reducing cost, the described component that contains alkene can select to contain the distillate of alkene, and the content of alkene is at least 30 heavy %, preferably hypotoxic alkane of other main ingredients in the distillate or naphthenic hydrocarbon in the distillate.For further reducing cost, it is that 170-350 ℃, olefin(e) centent are the distillate that the wax destructive distillation of the heavy % of 50-90 generates that the described component that contains alkene can be selected boiling point.
The used organic additive of the described vulcanization of rubber the Lv Shiguang chief editor " PP458-536 describes in detail in 1995 for plastic, rubber auxiliary agent handbook, China Light Industry Press.Described auxiliary agent preferred rubber is vulcanized one or more in used metal-free organic additive.Wherein, more preferably: one or more in the following compound: tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, tetramethylthiuram tetrasulfide, the 2-benzothiazolyl mercaptan, dibenzothiazyl disulfide, N, N-di-isopropyl-2-[4-morpholinodithio sulphenamide, N tert butyl benzothiazole 2 sulfenamide, N cyclohexyl 2 benzothiazole sulfenamide, N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide, N, O-two (1, the 2-ethylidene)-the 2-[4-morpholinodithio sulphenamide, 1, the 2-ethylene thiourea, N, N-di-n-butyl thiocarbamide, diphenyl thiourea, curing di-n-butyl xanthogenic acid, vulkacit D, di-o-tolylguanidine, triphenyl guanidine, N, O-two (1, the 2-ethylidene) thiocarbamyl-N, the inferior sulfanilamide (SN) of O-two (ethylene).The molecular formula of these compounds " has been made detailed description in the plastic, rubber auxiliary agent handbook above-mentioned.
According to method provided by the invention, described hydrogenation catalyst refers to that with inorganic refractory oxides (as aluminum oxide, silicon oxide, silica-alumina) be carrier, a kind of in the hydrotreatment of one or more in load regulation VIII family metal oxide, the group vib metal oxide, hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), the catalytic hydro-dearomatization catalyst or be carrier with zeolite and heat-resistant inorganic oxide, the hydrocracking catalyst of one or more in load regulation VIII family metal oxide, the group vib metal oxide.Preferred hydrogenation catalyst is to be carrier with inorganic refractory oxides (as aluminum oxide, silicon oxide, silica-alumina), a kind of in the hydrotreatment of one or both in one or both in nickel-loaded, the cobalt/cobalt oxide and molybdenum, the tungsten oxide, hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), the catalytic hydro-dearomatization catalyst or be carrier with zeolite and heat-resistant inorganic oxide, the hydrocracking catalyst of one or both in one or both in nickel-loaded, the cobalt/cobalt oxide and molybdenum, the tungsten oxide.Can also contain cocatalyst component such as fluorine, phosphorus, boron in the described catalyzer.
Described inert atmosphere in the prior art, as existing description the among the CN1262305A, in general, described inert atmosphere refer to not with catalyzer in any one gas or the gaseous mixture atmosphere of component generation chemical reaction, as helium-atmosphere, neon atmosphere, argon atmospher, nitrogen atmosphere, carbon dioxide atmosphere etc.Preferred nitrogen atmosphere wherein.Described inert atmosphere can be the mobile inert atmosphere, also can be static inert atmosphere.Under the preferable case, described inert atmosphere is static inert atmosphere, is about to catalyzer behind the solution of Containing Sulfur alkene that dipping is dissolved with elementary sulfur with described inert atmosphere, carries out heat treated under airtight condition.The pressure of described rare gas element can be normal pressure, be lower than normal pressure or be higher than normal pressure, still, preferably at normal pressure or be higher than under the normal pressure and carry out, more preferably carries out under the pressure of 0.1-5 MPa.
The condition of heatable catalyst is in prior art under inert atmosphere, and as existing description the among the CN1262305A, the temperature of heating is 100-300 ℃, is preferably 150-250 ℃, and be at least 1 hour heat-up time, is preferably 2-5 hour.
According to method provided by the invention, catalyzer is carried out the catalyzer that prevulcanized obtains must pass through activation treatment before use, make the hydrogenation active metals oxygenate conversion on the catalyzer become sulphided state.The method of deactivated catalyst can adopt conventional method, as can catalyzer being contacted at least 0.5 hour with hydrogen, preferred 0.5 hour to 3 days under greater than 200 ℃, preferred 200-450 ℃ condition in temperature.The method of deactivated catalyst also can slowly heatable catalyst be to the required temperature of hydrogenating desulfurization, denitrogenation or hydrocracking reaction under the condition that hydrogen exists, and this temperature is generally between 200-450 ℃.
Following example will the present invention will be further described, but not thereby limiting the invention.
Example 1
This example illustrates method provided by the invention.
(1) with 200 gram wax olefin crackings (the name of product order alkene of attaching most importance to, Beijing Yanshan Petrochemical company limited chemical industry two factory's products, contain paraffinic hydrocarbons 19.4 heavy %, monoolefine 65.6 heavy %, diolefin 12.8 heavy %, the heavy % of aromatic hydrocarbons 2.2, boiling spread is 254-382 ℃, the proportion under 20 ℃ is 0.8406 gram per centimeter
3, be 1 calculating by the mol ratio of olefinic double bonds and elementary sulfur, the elementary sulfur consumption is 12.7 gram elementary sulfurs/100 gram wax olefin crackings, 200 gram alkene should be 25.4 gram sulphur, for making the excessive elementary sulfur of adding that reacts completely.Promptly 34 Powdered elementary sulfurs of gram and the Powdered tetramethyl-thiuram disulfide of 6 grams mix, and in the three-necked bottle of again mixture being packed into, under agitation in 180 ℃ of reactions 1 hour, obtain the solution of Containing Sulfur alkene, and the sulphur content in the solution of Containing Sulfur alkene is 15.0 heavy %.Wherein, the sulphur of 11.0 heavy % exists with the form of olefine sulfide, and the sulphur of 4.0 heavy % exists with the form of dissolved elementary sulfur, the SLFA-920 type X ray sulphur detector analysis that the sulphur content in the Containing Sulfur olefin solution is produced with Japanese HORIBA company.
(2) take by weighing the solution that 4 gram elementary sulfurs and 26 grams (1) go on foot the Containing Sulfur alkene that obtains, in beaker, mix,, elementary sulfur is dissolved fully, must be dissolved with the solution of the Containing Sulfur alkene of elementary sulfur 140 ℃ of heating.The total content of sulphur (in elementary sulfur) is 26.3 heavy % in the solution, is 1.8 with the weight ratio of elementary state sulphur that exists and the sulphur that exists with olefine sulfide.
(3) be that solution and the 100 gram temperature of 140 ℃ the Containing Sulfur alkene that is dissolved with elementary sulfur are that 140 ℃ three leaf bar shaped commercial catalysts CH-7 (contain nickel oxide 2.5 weight % with (2) temperature that obtains of step, Tungsten oxide 99.999 26.4 heavy %, fluorine 5.9 heavy %, 0.33 milliliter/gram of water hole volume, the circumscribed circle diameter of three leaf bar shapeds is 1.2 millimeters, the long 3-8 millimeter of bar, Chang Ling refinery catalyst plant is produced) mix, stir.
(4) product that (3) step was obtained places a stainless steel reactor, the air in the usefulness normal pressure nitrogen replacement reactor three times, then, close terminal valve, under air-tight state, to handle 3 hours in 205 ℃ of constant temperature, the pressure that is warming up to system after 205 ℃ rises to about 0.8 MPa.Be cooled to room temperature, the catalyzer C after obtaining vulcanizing
1
With the catalyzer C after the sulfuration that obtains
1Weigh, its weight is designated as W
1, via diameter is 0.9 millimeter a sieve then, again with the catalyzer C of particle diameter less than 0.9 millimeter
1Weigh, its weight is designated as W
2, the percentage of damage=W of catalyzer then
2/ W
1Catalyzer C
1Percentage of damage and sulphur content list in the table 1.Sulphur content adopts high-frequency combustion-infrared detection method to measure (analytical instrument is the CS-444 determination of carbon and sulfur instrument of U.S. Leco company).
Comparative Examples 1
By the CN1262305A disclosed method catalyzer is carried out prevulcanized.
(1) takes by weighing in the Kjeldahl flask of packing into after 100 gram example 1 described catalyzer CH-7 and the Powdered elementary sulfur of 4 grams mix, go out air three times in the Kjeldahl flask, seal bottleneck then with nitrogen replacement.Kjeldahl flask is fixed on the motor drive shaft, and flask prolongs horizontal aspect and inserts in the saggar, opens motor, and regulating rotating speed is 10 rev/mins, is warming up to 110 ℃ with 6 ℃/minute speed, constant temperature 1 hour, and cooling obtains the dried catalyzer that soaks elementary sulfur.
(2) the dried catalyzer that soaks elementary sulfur that (1) step was obtained at room temperature goes on foot solution 26 grams that obtain Containing Sulfur alkene with example 1 (1) to be mixed, and stirs.
(3) method of pressing (4) step in the example 1 is handled catalyzer, measures the catalyst B after the reference that obtains vulcanizes
1Percentage of damage and sulphur content, the results are shown in Table 1.
Example 2
This example illustrates method provided by the invention.
Method by example 1 is carried out prevulcanized to same catalyzer, and different is that handling catalyst temperature under nitrogen atmosphere is 190 ℃, the catalyzer C after obtaining vulcanizing
2Catalyzer C
2Percentage of damage and sulphur content list in the table 1.
Comparative Examples 2
Press the CN1262305A disclosed method, catalyzer is carried out prevulcanized.
Method by Comparative Examples 1 is carried out prevulcanized to same catalyzer, and different is that the temperature of handling catalyzer under nitrogen atmosphere is 190 ℃, the reference catalyst B after must vulcanizing
2B
2Percentage of damage and sulphur content list in the table 1.
Example 3
This example illustrates method provided by the invention.
Method by example 1 is carried out prevulcanized to same catalyzer, the middle Powdered elementary sulfur of 37 grams that adds that feeds intake of different just (1) olefine sulfide preparations, adding assistant not, (2) consumption of elementary sulfur is respectively 4 grams and 7 gram elementary sulfurs in, be respectively 110 ℃ and 120 ℃ with 26 temperature that restrain the solution mixing post-heating of Containing Sulfur alkene, be dissolved with in the solution of Containing Sulfur alkene of elementary sulfur, the total content of sulphur (in elementary sulfur) is respectively 26.3 heavy % and 33.0 heavy %, weight ratio with elementary state sulphur that exists and the sulphur that exists with olefine sulfide is respectively 2.8 and 4.2, when being dissolved with the solution of Containing Sulfur alkene of elementary sulfur and catalyst mix (being steeping process), the temperature of described solution is respectively 110 ℃ and 120 ℃, the temperature of catalyzer also is respectively 110 ℃ and 120 ℃, heat-treat condition is 190 ℃, 3 hours, but the former is the closed system behind the nitrogen replacement, at room temperature charges into normal pressure nitrogen, be warming up to 190 ℃, intrasystem pressure is about 0.7 MPa behind the constant temperature; The latter is the atmospheric flow system that outlet is opened wide behind the nitrogen replacement, the catalyzer C after obtaining vulcanizing
3And C
4Catalyzer C
3And C
4Percentage of damage and sulphur content list in the table 1.
Table 1
| Example number | The catalyzer numbering | Percentage of damage, % | Sulphur content, heavy % |
| ??1 | ????C 1 | ????0.3 | ????5.44 |
| Comparative Examples 1 | ????B 1 | ????3.0 | ????5.46 |
| ??2 | ????C 2 | ????0.21 | ????5.66 |
| Comparative Examples 2 | ????B 2 | ????2.8 | ????5.70 |
| ??3 | ????C 3 | ????0.26 | ????5.60 |
| ??4 | ????C 4 | ????0.35 | ????5.45 |
Example 5-8
The acetone extraction test.
Press the method for CN1262305A example 5, respectively to the catalyzer C after the sulfuration
1-C
4Carry out the acetone extraction test, measure acetone extracting front and back catalyzer C
1-C
4Sulphur content, and calculate sulphur reservation degree, the results are shown in Table 2.
Comparative Examples 3-4
The acetone extraction test.
By the method for example 5 and 6 catalyzer is carried out the acetone extraction test respectively, the different reference catalyst B that just use respectively
1And B
2Replaced C
1And C
2The results are shown in Table 2.
Table 2
| Example number | The catalyzer numbering | Sulphur content before the acetone test, % | Sulphur content after the acetone extracting, % | Sulphur reservation degree, % |
| ??5 | ??C 1 | ??5.44 | ??4.37 | ??91.4 |
| Comparative Examples 3 | ??B 1 | ??5.46 | ??4.87 | ??89.2 |
| ??6 | ??C 2 | ??5.66 | ??3.65 | ??64.5 |
| Comparative Examples 4 | ??B 2 | ??5.70 | ??3.55 | ??62.3 |
| ??7 | ??C 3 | ??5.60 | ??3.57 | ??63.8 |
| ??8 | ??C 4 | ??5.45 | ??3.49 | ??64.0 |
The result of table 1 and table 2 shows, adopts method provided by the invention that catalyzer is carried out prevulcanized, and the catalyst breakage rate after the sulfuration reduces significantly, meanwhile, has also improved the reservation degree of sulphur.
Example 9-10
The catalytic performance of the catalyzer after the method sulfuration provided by the invention is adopted in the explanation of this example.
Catalyzer C with example 1 preparation
1In 100 milliliters of reactors of medium-sized reaction unit of 100 milliliters of packing into, adopt the gaseous activation method that catalyzer is activated, promptly at room temperature feeding air speed is 150 hours
-1Hydrogen, be warming up to 320 ℃ in 12 hours, then constant temperature 1 hour under this temperature.Catalytic cracking diesel oil oil with sulfur-bearing 4046ppm, nitrogen 949ppm is that reaction raw materials carries out activity rating to catalyzer, and temperature of reaction is 330 or 350 ℃, reactive hydrogen dividing potential drop 3.2 MPas, liquid hourly space velocity 2 hours
-1, hydrogen to oil volume ratio is 350, reaction result is listed in the table 3.
Comparative Examples 5-6
The catalytic performance of the catalyzer after the sulfuration of pre existing sulfuration method is adopted in following Comparative Examples explanation.
Method by example 9-10 activates catalyzer, and adopts same stock oil evaluation of catalyst activity under identical condition, the different reference catalyst B that just use respectively
1Replaced C
1, B
2Replaced C
2, the results are shown in Table 3.
Table 3
| Example number | The catalyzer numbering | Temperature of reaction, ℃ | Desulfurization degree, heavy % | Denitrification percent, heavy % |
| ??9 | ??C 2 | ??330 | ??90.2 | ??56.1 |
| Comparative Examples 5 | ??B 1 | ??330 | ??89.1 | ??54.7 |
| ??10 | ??C 2 | ??350 | ??95.5 | ??63.2 |
| Comparative Examples 6 | ??B 2 | ??350 | ??94.6 | ??61.6 |
The result of table 3 shows, compares with the pre existing vulcanization process, adopts method for pre-sulphuration provided by the invention that catalyzer is carried out prevulcanized, and the catalyzer after the sulfuration has higher desulfurization and denitrification activity.
Claims (18)
1. the method for pre-sulphuration of a hydrogenation catalyst, this method comprises with a kind of hydrogenation catalyst of a kind of solution impregnation of Containing Sulfur alkene, under inert atmosphere, heat this catalyzer then, it is characterized in that, the solution of described Containing Sulfur alkene is that temperature is a room temperature to 220 ℃, be dissolved with the solution of the Containing Sulfur alkene of elementary sulfur, total amount with solution is a benchmark, in elementary sulfur, the total content that is dissolved with sulphur in the solution of Containing Sulfur alkene of elementary sulfur is the heavy % of 4-40, wherein, the sulphur that exists with elementary state is 0.5-7 with the weight ratio of the sulphur that exists with olefine sulfide, and the temperature of dipping is a room temperature to 220 ℃; With sulfuration back end hydrogenation catalyzer is benchmark, and in elementary sulfur, the consumption of the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur makes the sulphur that contains the heavy % of 1-7.5 in the hydrogenation catalyst after the sulfuration.
2. method according to claim 1 is characterized in that, the total content of sulphur is the heavy % of 10-35 in the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur, and described weight ratio with elementary state sulphur that exists and the sulphur that exists with olefine sulfide is 1-5.
3. method according to claim 1 is characterized in that, the total sulfur content of the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur is lower than 18 heavy %, and the temperature of described solution is a room temperature to 200 ℃, and the temperature of described dipping is a room temperature to 200 ℃.
4. method according to claim 1 is characterized in that, the total sulfur content of the solution of the described Containing Sulfur alkene that is dissolved with elementary sulfur is not less than 18 heavy %, and the temperature of described solution is 100-200 ℃, and the temperature of described dipping is 100-200 ℃.
5. method according to claim 4 is characterized in that, the temperature of described solution is 100-160 ℃, and the temperature of described dipping is 100-160 ℃.
6. method according to claim 1, it is characterized in that, the described solution that is dissolved with the Containing Sulfur alkene of elementary sulfur is prepared as follows: (1) mixes a kind of component and elementary sulfur that contains alkene, heating is described mixture 0.5-10 hour under 100-220 ℃ temperature, wherein, the mol ratio of elementary sulfur and olefinic double bonds is 1-1.5, the cooling or cooled product is not to room temperature, the product liquid that obtains is the solution of Containing Sulfur alkene; (2) solution with the Containing Sulfur alkene that obtains mixes with elementary sulfur, under 100-220 ℃ temperature, heat, make the elementary sulfur dissolving, obtain being dissolved with the product of the Containing Sulfur alkene of elementary sulfur, the consumption of the solution of elementary sulfur and Containing Sulfur alkene makes the total content of sulphur in the solution of the Containing Sulfur alkene that finally is dissolved with elementary sulfur be, in elementary sulfur, the heavy % of 4-40 is 0.5-7 with the weight ratio of elementary state sulphur that exists and the sulphur that exists with olefine sulfide.
7. method according to claim 6, it is characterized in that, (1) temperature of heating is 130-210 ℃ described in, be 0.5-5 hour heat-up time, (2) temperature of heating is 140-200 ℃ described in, and be 0.5-1 hour heat-up time, the consumption of the solution of elementary sulfur and Containing Sulfur alkene, the total content that makes sulphur in the solution of the Containing Sulfur alkene that finally is dissolved with elementary sulfur is the heavy % of 10-35, is 1-5 with the weight ratio of elementary state sulphur that exists and the sulphur that exists with olefine sulfide.
8. method according to claim 1, it is characterized in that, the described solution that is dissolved with the Containing Sulfur alkene of elementary sulfur is prepared as follows: (1) is with a kind of component that contains alkene, elementary sulfur and auxiliary agent mix, heating is described mixture 0.5-10 hour under 100-220 ℃ temperature, wherein, the mol ratio of elementary sulfur and olefinic double bonds is 1-1.5, auxiliary dosage be the elementary sulfur consumption greater than 0 to 80 heavy %, the cooling or not cooled product to room temperature, the product liquid that obtains is the solution of Containing Sulfur alkene, described auxiliary agent is selected from one or more of the organic additive that is used for the vulcanization of rubber, (2) solution with the Containing Sulfur alkene that obtains mixes with elementary sulfur, under 100-220 ℃ temperature, heat, make the elementary sulfur dissolving, obtain being dissolved with the solution of the Containing Sulfur alkene of elementary sulfur, the consumption of the solution of elementary sulfur and Containing Sulfur alkene, make the total content of sulphur in the solution of the Containing Sulfur alkene that finally is dissolved with elementary sulfur be, in elementary sulfur, the heavy % of 4-40 is 0.5-7 with the weight ratio of elementary state sulphur that exists and the sulphur that exists with olefine sulfide.
9. method according to claim 8, it is characterized in that, (1) temperature of heating is 130-210 ℃ described in, be 0.5-5 hour heat-up time, auxiliary dosage is the heavy % of the 10-50 of elementary sulfur consumption, (2) temperature of heating is 140-200 ℃ described in, be 0.5-1 hour heat-up time, the consumption of the solution of elementary sulfur and Containing Sulfur alkene, the total content that makes sulphur in the solution of the Containing Sulfur alkene that finally is dissolved with elementary sulfur is the heavy % of 10-35, is 1-5 with the weight ratio of elementary state sulphur that exists and the sulphur that exists with olefine sulfide.
10. according to claim 6 or 8 described methods, it is characterized in that the described component that contains alkene is one or more in pure liquid monoene, diene and the polyenoid.
11. method according to claim 10 is characterized in that, described alkene is the alkene that contains 5-30 carbon atom.
12., it is characterized in that according to claim 6 or 8 described methods, also contain in alkane, naphthenic hydrocarbon, the aromatic hydrocarbons one or more in the described component that contains alkene, olefin(e) centent is the heavy % of 30-100 in the described component that contains alkene.
13. method according to claim 12 is characterized in that, the described component that contains alkene is that boiling point is that 170-350 ℃, olefin(e) centent are the distillate that the wax destructive distillation of the heavy % of 50-90 generates.
14. method according to claim 8, it is characterized in that, described auxiliary agent is selected from one or more in the following compound: tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, tetramethylthiuram tetrasulfide, the 2-benzothiazolyl mercaptan, dibenzothiazyl disulfide, N, N-di-isopropyl-2-[4-morpholinodithio sulphenamide, N tert butyl benzothiazole 2 sulfenamide, N cyclohexyl 2 benzothiazole sulfenamide, N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide, N, O-two (1, the 2-ethylidene)-the 2-[4-morpholinodithio sulphenamide, 1, the 2-ethylene thiourea, N, N-di-n-butyl thiocarbamide, diphenyl thiourea, curing di-n-butyl xanthogenic acid, vulkacit D, di-o-tolylguanidine, triphenyl guanidine, N, O-two (1, the 2-ethylidene) thiocarbamyl-N, the inferior sulfanilamide (SN) of O-two (ethylene).
15. method according to claim 1, it is characterized in that, described hydrogenation catalyst refers to that with inorganic refractory oxides be carrier, hydrotreatment, hydrogenating desulfurization, hydrodenitrification, the hydrodemetallation (HDM) of one or more in load regulation VIII family metal oxide, the group vib metal oxide, a kind of in the catalytic hydro-dearomatization catalyst or be carrier with zeolite and heat-resistant inorganic oxide, the hydrocracking catalyst of one or more in load regulation VIII family metal oxide, the group vib metal oxide.
16. method according to claim 15, it is characterized in that, described hydrogenation catalyst is for being carrier with inorganic refractory oxides, a kind of in the hydrotreatment of one or both in one or both in nickel-loaded, the cobalt/cobalt oxide and molybdenum, the tungsten oxide, hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), the catalytic hydro-dearomatization catalyst or be carrier with zeolite and heat-resistant inorganic oxide, the hydrocracking catalyst of one or both in one or both in nickel-loaded, the cobalt/cobalt oxide and molybdenum, the tungsten oxide.
17. method according to claim 1 is characterized in that, described inert atmosphere is a nitrogen atmosphere.
18. method according to claim 1 is characterized in that, the temperature of heatable catalyst is 150-250 ℃ under inert atmosphere, and be 2-5 hour heat-up time.
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| CN100413588C (en) * | 2005-05-12 | 2008-08-27 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition and its prepn. method |
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| CN107457006B (en) * | 2016-06-03 | 2020-06-12 | 中国石油化工股份有限公司 | Hydrogenation catalyst, pretreatment method thereof, method for improving desulfurization activity of hydrogenation catalyst and application |
| CN107456975B (en) * | 2016-06-03 | 2020-06-16 | 中国石油化工股份有限公司 | Hydrogenation catalyst, pretreatment method thereof, method for improving desulfurization activity of hydrogenation catalyst and application |
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