CN101618353B - Method for activating hydrogenation catalyst - Google Patents
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- CN101618353B CN101618353B CN 200810012215 CN200810012215A CN101618353B CN 101618353 B CN101618353 B CN 101618353B CN 200810012215 CN200810012215 CN 200810012215 CN 200810012215 A CN200810012215 A CN 200810012215A CN 101618353 B CN101618353 B CN 101618353B
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Abstract
The invention discloses a method for activating a hydrogenation catalyst, which comprises the steps of filling a porous proppant composition and a hydrogenation catalyst into a reactor respectively and activating the hydrogenation catalyst. The porous proppant composition comprises the following components: (1) a porous proppant, (2) sulfur, (3) an organic solvent and (4) an assistant, wherein the sulfur in form of sulfur element is 20 to 300 percent by weight of the porous proppant; the organic solvent is 0 to 50 percent by weight of the porous proppant; and the assistant is 0 to 25 percent by weight of the porous proppant. In the method, the adoption of the porous proppant composition for providing the hydrogenation catalyst with a vulcanizing agent can reduce the working time of devices, improve product efficiency, overcome a drawback of in-situ presulfurization, dissipate heat generated in a reactivation process and avoid local overheating of a presulfurization hydrogenation catalyst bed layer, so the influences on the catalyst performance are reduced.
Description
Technical field
The present invention relates to the method for pre-sulphuration of a kind of activation method of hydrogenation catalyst, particularly hydrogenation catalyst.
Background technology
Industrial used hydrogenation catalyst generally is to be carrier with refractory oxides such as aluminium oxide, sial, molecular sieves, with in group vib metal (as molybdenum, tungsten) and the group VIII metal (as cobalt, nickel) one or more is active metal component, and these active metal components are to be dispersed on the carrier with oxidation state, and in hydrogenation process, the activity of such catalysts metal component is in sulphided state, and (metal exists with oxide morphology: Co
9S
8, MoS
2, Ni
3S
2, WS
2Deng) time have higher active and stable.Therefore, before catalyst uses, need to carry out presulfurization, change reactive metal into sulphided state from oxidation state.These hydrogenation catalysts mainly comprise Hydrobon catalyst, hydrocracking catalyst and catalyst for hydro-upgrading.
At present, the method for pre-sulphuration of hydrogenation catalyst mainly comprises two classes: the outer presulfurization of presulfurization and device in the device.
Presulfurization is that oxidation catalyst is loaded into reactor in the device, and then the vulcanizing agent injecting reactor vulcanized, this is the method that often adopts, its weak point mainly is the on-the-spot supporting vulcanizing equipment that needs that goes into operation, vulcanizing agent pollutes plant area, and cure time is longer, influences the production efficiency of process units.In order to address the above problem, CN 1299706A adopts presulfurization new technology in a kind of built-in device, the oxidation state hydrogenation catalyst is filled in the hydrogenation reactor, and get a certain amount of (by the hydrogenation catalyst complete cure in theory needed amount 0.5-2.0 doubly) solid sulfurizing agent be seated in the top of hydrogenation reactor, join the hydrogen presulfurization with nitrogen do carrier gas then.CN 1286290A patent be with solid sulfurizing agent and oxidation state tungsten-nickel series hydrogenating catalyst for refining layering in catalyst: the vulcanizing agent weight ratio is 4: 1～20: 1 the ratio hydrogenation reactor of packing into jointly, joins the hydrogen presulfurization with nitrogen do carrier gas then.Above-mentioned two patented methods all are that solid sulfurizing agent is seated in separately on the oxidation state hydrogenation catalyst bed, and these vulcanizing agents account for bigger space in hydrogenation reactor, thereby influence the treating capacity of device.
Before the outer presulfurization of catalyst device was meant filling, catalyst cured, partial vulcanization or hold certain vulcanizing agent.After being loaded in the hydrogenation reactor, this catalyst need not to inject the method for vulcanizing agent.The on-stream time of the outer pre-sulfide catalyst of device is short than presulfurization in the device, has improved the production efficiency of device, has overcome the shortcoming of presulfurization in the device.
The outer pre-curing technology of device has two kinds of routes: the first changes the reactive metal on the catalyst into sulphided state fully, and passivation is used then; It two is to add vulcanizing agent before catalyst is loaded into reactor, in reactor reactive metal is converted into sulphided state then.USP4943547, USP5215954 etc. with elemental sulfur join generate in advance in higher boiling oil or the organic solvent suspension again with the fresh catalyst effect, or contact the back with fresh catalyst at the powdery elemental sulfur and soak into higher boiling oil or organic solvent.USP6077803 is dissolved in elemental sulfur and organic sulfur in the solvent, under the condition that stabilizing agent organic acid, mercaptan or organic alcohols exist, is under the stabilizing agent condition at glycerine or hexose particularly simultaneously, and element sulphur is introduced catalyst.The purpose of the outer presulfurization of above-mentioned catalyst device is under the situation of not introducing other vulcanizing agent, guarantees this catalyst self full cure.The outer pre-sulfide catalyst heat release in activation process of device mainly comes from two parts, and a part of heat is to derive from vulcanizing agent and hydrogen reaction generation hydrogen sulfide process; Another part heat is to derive from reactive metal oxides and hydrogen sulfide reaction generation metal sulfide process, and these heats can make beds produce bigger temperature rise, thereby makes the difficult control of activation process of catalyst.
Hydrogenation reactor is interior except adopting hydrogenation catalyst, usually all to load proppant at hydrogenation catalyst bed top and bottom, that these proppants have is high temperature resistant, the characteristic of high pressure and high mechanical properties, plays a part covering, support catalyst and filtration, dispersion vapour-liquid.Porous propping agent has stronger appearance impurity ability, thereby has protected main hydrogenating catalyst, has prolonged the device on-stream time.Porous propping agent does not generally contain reactive metal, is referred to as inert proppant such as CN1120971A, perhaps contains a spot of reactive metal, is referred to as active proppant.Reactive metal in the active proppant is generally one or more in VIB and/or the group VIII metal, is preferably in cobalt, molybdenum, nickel and the tungsten one or more.At present, do not see report as yet about the sulfur-bearing porous propping agent.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of activation method of hydrogenation catalyst, this method not only can provide vulcanizing agent for hydrogenation catalyst, and compare with method for pre-sulphuration in the conventional device, can the curtailment of operation, compare with the outer method for pre-sulphuration of conventional device, can disperse heat release, reduce influence catalyst performance.
Hydrogenation catalyst activation method of the present invention comprises:
(A) respectively porous propping agent combination and hydrogenation catalyst are packed in the reactor;
(B) activation hydrogenation catalyst;
The porous propping agent combination described in the step (A) wherein, its composition comprises following component:
(1) porous propping agent;
(2) sulphur in element sulphur, accounts for 20%～300% of porous propping agent weight, is preferably 50%～280%;
(3) organic solvent accounts for 0～50% of porous propping agent weight, is preferably 0%～30%;
(4) auxiliary agent accounts for 0～25.0% of porous propping agent weight, is preferably 0.5%～25%, is preferably 2.0%～10.0%.
The sulfur content of described porous propping agent combination is enough to make the full cure of oxidation state hydrogenation catalyst, and then hydrogenation catalyst all adopts the hydrogenation catalyst of oxidation state; Wherein said full cure is meant that the sulfur content of porous propping agent combination is theoretical 80%～200% of the sulfur content that needs of hydrogenation active metals in porous propping agent combination and the hydrogenation catalyst, is preferably 85%～120%.
The sulfur content deficiency of described porous propping agent combination is so that under the situation of oxidation state hydrogenation catalyst full cure, just need alternate manner in reactor, to replenish sulphur, among the present invention described hydrogenation catalyst is adopted the hydrogenation catalyst of the outer presulfurization of device, the hydrogenation catalyst of the outer presulfurization of device and the total sulfur content that porous propping agent combination provides make the hydrogenation catalyst full cure; Wherein said full cure is meant that the hydrogenation catalyst of the outer presulfurization of device and total sulfur content that carries of porous propping agent combination are theoretical 80%～200% of the sulfur contents that needs of hydrogenation active metals in porous propping agent combination and the hydrogenation catalyst, is preferably 85%～120%.
The theory of hydrogenation active metals need sulfur content be that contained hydrogenation metal component is converted into corresponding sulfide (Co on porous propping agent combination and the hydrogenation catalyst in described porous propping agent combination and the hydrogenation catalyst
9S
8, MoS
2, Ni
3S
2, WS
2) time need the amount of sulphur.
The described activation hydrogenation catalyst of step (B) can adopt conventional wet method sulfuration, generally comprise nitrogen replacement, draw hydrogen and set up hydrogen circulation, introduce that sulfurized oil is prewetted to catalyst and the sulfuration of catalyst, wherein used sulfurized oil is one or more in the distillates such as gasoline, kerosene and diesel oil.Sulfurized oil is introduced reactor carry out catalyst when prewetting, the control reactor inlet temperature is 130～160 ℃, volume space velocity 0.2～20h
-1The following condition of the general employing of the sulfuration of described catalyst: pressure 1～20MPa, H
2Air speed is 100～10000h
-1, 5～60 ℃/h of programming rate, the reactor inlet final temperature is 200 ℃～400 ℃, is preferably 280～360 ℃, and under this temperature constant temperature 2～36 hours.
In the step (A), the filling ratio of porous propping agent combination and hydrogenation catalyst and loading position are identical with the filling ratio and the loading position of conventional porous propping agent and hydrogenation catalyst, and those skilled in the art can determine according to general knowledge.Porous propping agent combination can be seated in the upstream of hydrogenation catalyst, also porous propping agent can be seated in simultaneously the upstream and downstream of hydrogenation catalyst.
Porous propping agent described in the present invention can be for not containing the inertia porous propping agent of reactive metal, also can be for containing the active porous proppant of a small amount of reactive metal, wherein the content of reactive metal accounts for below 2.0% of porous propping agent weight in oxide, is preferably 0.01%～2.0%.Described inertia porous propping agent is one or more in the porous refractory inorganic oxides such as aluminium oxide, silica, titanium oxide, zirconia, zinc oxide.Described active porous proppant is a small amount of reactive metal of load on one or more in porous refractory inorganic oxides such as aluminium oxide, silica, titanium oxide, zirconia, zinc oxide.Described reactive metal is one or more in VIB and/or the group VIII metal, is preferably in cobalt, molybdenum, nickel and the tungsten one or more.
Used vulcanizing agent when the sulphur in the described porous propping agent combination derives from the outer presulfurization hydrogenation catalyst of existing preparing device can be in elemental sulfur, inorganic sulphide and the organic sulfur compound one or more, preferably comes from elemental sulfur.Wherein inorganic sulphide can be carbon disulfide, and organic sulfur compound can be selected from the organic polysulfide described in mercaptan, thioether, disulphide and the CN1611577A.
In the porous propping agent combination, described auxiliary agent is preferably the thiurams material, accounts for 0～25.0% of porous propping agent weight, is preferably 0.5%～25.0%, is preferably 2.0%～10.0%.
Thiurams material wherein is the compound that contains nitrogen and sulphur, as tetrabutylthiuram disulfide (TBTD), tetra-benzyl thiram disulfide, DMDPTD dimethyl diphenylthiuram disulfide, tetraethylthiuram disulfide, DMDPTD dimethyl diphenylthiuram disulfide (TM), tetraethylthiuram disulfide (TETD), tetramethylthiuram monosulfide (TMTM), diethyl diphenyl thiuram disulfide (TE) and tetramethylthiuram disulfide (TMTD) etc., and in other material close with the above-mentioned substance structure one or more.
Wherein organic solvent can adopt some commonly used organic solvents of this area, as in hydrocarbon ils and the organic carboxylic ester one or more.Hydrocarbon ils generally can be from the heavy end wet goods of various naphthas, gasoline, kerosene, diesel oil, white oil, lube base oil, straight run and decompression one or more, the hydrocarbon ils that obtains of secondary operations preferably, the above-mentioned hydrocarbon ils that obtains as technologies such as catalytic cracking, thermal cracking.Organic carboxylic ester can be the organic carboxylic ester that contains 6～60 carbon atoms, the preferred fat acid glyceride, as sesame oil, safflower seed oil, corn oil, cottonseed oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut oil, olive oil, sunflower oil, lard, n-butyl acetate, 1-Methoxy-2-propyl acetate, 1, the 4-butanediol diacrylate, the cyclohexylenedinitrilotetraacetic acid isopropyl ester, hexa-methylene-1,6 vulcabond, triethyl phosphate, methyl phenylacetate, isobutyl phenylacetate, the terephthalic acid (TPA) dinonyl, repefral, diethyl phthalate, Methyl Salicylate, butyl p-hydroxybenzoate, and in similar other organic carboxylic ester etc. one or more.
Can also contain other additive in the porous propping agent combination, as organic carboxylic-acid substance, organic alcohols material, organic ketone material etc. one or more, its content can be 0.5%～15.0% of porous propping agent combination weight.
The concrete preparation process of porous propping agent combination of the present invention is as follows:
(1) gets porous propping agent;
(2) according to the proportioning of porous propping agent combination, in porous propping agent, introduce sulphur, organic solvent and auxiliary agent.
Among the present invention, the mode that sulphur is introduced in the porous propping agent is selected according to the type of vulcanizing agent, when using elemental sulfur to make vulcanizing agent, can adopt the introducing method that the presulfurization hydrogenation catalyst is used always outside the device in the prior art, flood, be dispersed in impregnating in the organic solution as distillation absorption, fusing.Adopting other vulcanizing agent except that elemental sulfur generally is to adopt infusion process to introduce.
Among the present invention, described auxiliary agent, organic solvent and other additive can adopt infusion process to introduce porous propping agent.
Auxiliary agent in the step (2) wherein, the method that organic solvent and vulcanizing agent are introduced hydrogenation catalyst can adopt various orders, introduce auxiliary agent earlier as (1), introduce vulcanizing agent then, introduce organic solvent at last, or (2) introduce auxiliary agent earlier, introduce organic solvent then, introduce vulcanizing agent at last, or (3) introduce auxiliary agent earlier, then vulcanizing agent and organic solvent are introduced simultaneously, or (4) introduce organic solvent earlier, introduce vulcanizing agent then, introduce auxiliary agent at last, or (5) introduce vulcanizing agent earlier, introduce auxiliary agent then, introduce organic solvent at last, or (6) introduce vulcanizing agent earlier, introduce organic solvent then, introduce auxiliary agent at last, or (7) introduce vulcanizing agent earlier, organic solvent and auxiliary agent are introduced simultaneously then, or (8) introduce organic solvent earlier, vulcanizing agent and auxiliary agent are introduced simultaneously then, or (9) introduce organic solvent earlier, introduce auxiliary agent then, introduce vulcanizing agent at last, or (10) three mixing introducing simultaneously, or other various orders.The introducing method of various materials and order can be determined by this area general knowledge by Substance Properties.Auxiliary agent thiurams material is introduced in the porous propping agent after preferably adopting and being dissolved in solvent, solvent such as benzene, acetone and chloroform etc. commonly used, can remove with the method for evaporation then and desolvate, generally can be 80 ℃～200 ℃ of temperature, preferably between 80 ℃～140 ℃, evaporate to remove and desolvate, time was generally 1～20 hour, preferred 2～8 hours.
After introducing auxiliary agent, vulcanizing agent and organic solvent, can carry out heat treated, the interaction of adding material and proppant is strengthened, relax and release sulphur, reduce and run off.Heating condition is generally 50～300 ℃ and handled 1～40 hour down.Heat treated atmosphere can be that inert gas, oxygen content are in oxygen atmosphere and the water vapour one or more of having of 0.1v%～30v%.
Described hydrogenation catalyst comprises one or more in Hydrobon catalyst, hydrocracking catalyst, the catalyst for hydro-upgrading.Be active metal component generally, be preferably among W, Mo, Ni and the Co one or more, be generally 3wt%～50wt% in oxide hydrogenation activity constituent content with in VIB and/or the group VIII metal one or more.Carrier is a refractory inorganic oxides, as in aluminium oxide, silica, titanium oxide, zirconia, the molecular sieve one or more, also can contain conventional auxiliary agent, such as in phosphorus, boron, the fluorine etc. one or more.
The outer presulfurization hydrogenation catalyst of described device can adopt the hydrogenation catalyst of any method sulfuration in the prior art, the outer pre-sulfide catalyst of device that obtains such as disclosed vulcanization process in the patents such as CN1769377A, CN1861259A, CN1861260A.Year sulfur content of the outer pre-sulfide catalyst of this device can be determined according to porous propping agent combination sulfur content and hydrogenation active metals amount.
In the inventive method, outside adopting device during the presulfurization hydrogenation catalyst, hydrogenation catalyst all can be adopted the outer presulfurization hydrogenation catalyst of device, also hydrogenation catalyst can be adopted partial oxidation attitude hydrogenation catalyst, part adopts the outer presulfurization hydrogenation catalyst of device, and both evenly mix back filling or layering filling.Wherein said layering filling is the upstream that the hydrogenation catalyst of presulfurization is contained in the oxidation state hydrogenation catalyst.
In the inventive method, used porous propping agent combination provides all or part of vulcanizing agent for hydrogenation catalyst, compare with presulfurization in the conventional device, can shorten the on-stream time of device, enhance productivity, compare with the outer presulfurization of conventional device, the heat that vulcanizing agent that porous propping agent combination provides and hydrogen reaction generate concentrates on the proppant part, shared the part heat, thereby make hydrogenation catalyst in activation process, disperse heat release, avoid hydrogenation catalyst bed local temperature too high, influence catalyst performance.In addition, compare with CN 1299706A with CN 1286290A, the sulphur of introducing in the porous propping agent mainly is distributed in the duct of proppant, can't increase the volume of proppant, thereby can not influence the treating capacity of device.
Porous propping agent combination of the present invention does not have pyrophorisity, is easy to store, transports and uses.Porous propping agent combination preparation process of the present invention is simple, and production cost is low, is suitable for extensive use.
Porous propping agent combination of the present invention preferred auxiliary agent thiurams material of introducing in preparation process not only can promote contacting of vulcanizing agent and proppant, make and slowly discharge sulphur in the catalyst activation process constantly, avoid concentrating heat release, reduce influence the hydrogenation catalyst catalytic performance.
The specific embodiment
Below in conjunction with embodiment the inventive method and effect are described further, but do not limit the scope of the invention.
The preparation method of aluminum oxide porous proppant SA1, SA2, SA3 sees CN1120971A embodiment 1, embodiment 3 and embodiment 5 respectively, and its character sees Table 1.
The aluminum oxide porous proppant character of table 1
| Project | SA1 | SA2 | SA3 |
| Bulk density, g/ml | 0.45 | 0.51 | 0.63 |
| Crushing strength, the N/ grain | 61 | 44 | 92 |
| Total pore volume, ml/g (pressure mercury) | 1.098 | 0.928 | 0.732 |
Embodiment 1
Porous propping agent combination CA1 preparation process is as follows:
The elemental sulfur of fusing is introduced aluminum oxide porous proppant SA1 with infusion process, and the introducing amount of elemental sulfur is 180% of a porous propping agent weight.Then tetrabutylthiuram disulfide (TBTD) is mixed with heavy diesel fuel, this mixture is contained in the porous propping agent of elemental sulfur with the infusion process introducing, the TBTD consumption is 3% of a porous propping agent weight, and the heavy diesel fuel consumption is 20% of a porous propping agent weight.In normal pressure, moving air atmosphere not, handled 5 hours, and obtained porous propping agent combination CA1 for 160 ℃ at last.
Embodiment 2
Porous propping agent combination CA2 preparation process is as follows:
Tetramethylthiuram disulfide (TMTD) is dispersed in the organic solvent (peanut oil and 4: 1 mixture of heavy diesel fuel weight ratio), elemental sulfur is dispersed in the said mixture, this impregnation mixture method is introduced among the porous propping agent SA2, the introducing amount of elemental sulfur is 60% of a porous propping agent weight, the TMTD consumption is 2% of a porous propping agent weight, and consumption of organic solvent is 15% of a porous propping agent weight.In normal pressure, moving air atmosphere not, handled 5 hours, and obtained porous propping agent combination CA2 for 160 ℃ at last.
Embodiment 3
Porous propping agent combination CA3 preparation process is as follows:
The elemental sulfur of fusing is introduced aluminum oxide porous proppant SA3 with infusion process, and the introducing amount of elemental sulfur is 270% of a porous propping agent weight.Just tetramethylthiuram disulfide (TMTD) is dissolved in benzene then, this mixture is introduced with infusion process contain in the catalyst of elemental sulfur, and the TMTD consumption is 5% of a porous propping agent weight.At last in normal pressure, water vapour and volume of air than under 5: 1 atmosphere, handled 5 hours at 120 ℃, obtain porous propping agent combination CA3.
Embodiment 4
Porous propping agent combination CA4 preparation process is as follows:
The elemental sulfur of fusing is introduced among the aluminum oxide porous proppant SA1 with infusion process, the introducing amount of elemental sulfur is 160% of a porous propping agent weight, then it is added in the kerosene, the kerosene consumption is 15% of a porous propping agent weight, obtains porous propping agent combination CA4.
Embodiment 5
Porous propping agent combination CA5 preparation process is as follows:
Carbon disulfide and uncle's nonyl sulfide (TNPS) are mixed, and the weight ratio of carbon disulfide and uncle's nonyl sulfide is 1: 3, and the introducing amount (in element sulphur) of vulcanizing agent is 100% of a porous propping agent weight.With infusion process above-mentioned vulcanizing agent is introduced among the porous propping agent SA2 then.At normal pressure, in water vapour and the Air mixing atmosphere, handled 6 hours down at last, obtain porous propping agent combination CA5 at 50 ℃.
Embodiment 6
Porous propping agent combination CA6 preparation process is as follows:
DMDPTD dimethyl diphenylthiuram disulfide is dissolved in the benzene, be immersed on the porous propping agent SA1, the DMDPTD dimethyl diphenylthiuram disulfide addition is 4% of a porous propping agent weight, then 110 ℃ of dryings 3 hours, solvent evaporated benzene obtains the porous propping agent of load DMDPTD dimethyl diphenylthiuram disulfide.Then the elemental sulfur of fusing is introduced in the above-mentioned porous propping agent that contains DMDPTD dimethyl diphenylthiuram disulfide, the introducing amount of elemental sulfur is 60% of a porous propping agent weight.Add then in n-butyl acetate, 2: 6 the mixture of heavy diesel fuel weight ratio, its consumption is 6% of a porous propping agent weight, obtains porous propping agent combination CA6.
Embodiment 7
The outer pre-sulfide catalyst SCAT-A1 of device of preparation Hydrobon catalyst A (it is formed and character sees Table 2), process is as follows: the elemental sulfur of fusing is introduced Hydrobon catalyst A, and the introducing amount of elemental sulfur is theoretical 120% of the sulfur content that needs of Hydrobon catalyst A.Then tetrabutylthiuram disulfide (TBTD) is mixed with heavy diesel fuel, this mixture is contained in the catalyst of elemental sulfur with the infusion process introducing, the TBTD consumption is 3% of a catalyst weight, and the heavy diesel fuel consumption is 20% of a catalyst weight.At normal pressure, not moving air and water vapor mixture atmosphere, handled 5 hours for 160 ℃ at last, obtain the outer pre-sulfide catalyst SCAT-A1 of device.
Embodiment 8
The outer pre-sulfide catalyst SCAT-B1 of device of preparation hydrocracking catalyst B (it is formed and character sees Table 3), process is as follows: the elemental sulfur of fusing is introduced hydrocracking catalyst B, and the introducing amount of elemental sulfur is theoretical 60% of the sulfur content that needs of hydrocracking catalyst B.Then tetrabutylthiuram disulfide (TBTD) is mixed with heavy diesel fuel, this mixture is contained in the catalyst of elemental sulfur with the infusion process introducing, the TBTD consumption is 3% of a catalyst weight, and the heavy diesel fuel consumption is 20% of a catalyst weight.At normal pressure, not moving air and water vapor mixture atmosphere, handled 5 hours for 160 ℃ at last, obtain the outer pre-sulfide catalyst SCAT-B1 of device.
Embodiment 9
The outer pre-sulfide catalyst SCAT-A2 of device of preparation Hydrobon catalyst A (it is formed and character sees Table 2), process is as follows: the elemental sulfur of fusing is introduced Hydrobon catalyst A, and the introducing amount of elemental sulfur is theoretical 90% of the sulfur content that needs of Hydrobon catalyst A.Then tetrabutylthiuram disulfide (TBTD) is mixed with heavy diesel fuel, this mixture is contained in the catalyst of elemental sulfur with the infusion process introducing, the TBTD consumption is 3% of a catalyst weight, and the heavy diesel fuel consumption is 20% of a catalyst weight.At normal pressure, not moving air and water vapor mixture atmosphere, handled 5 hours for 160 ℃ at last, obtain the outer pre-sulfide catalyst SCAT-A2 of device.
Embodiment 10
The outer pre-sulfide catalyst SCAT-B2 of device of preparation hydrocracking catalyst B (it is formed and character sees Table 3), process is as follows: the elemental sulfur of fusing is introduced hydrocracking catalyst B, and the introducing amount of elemental sulfur is theoretical 120% of the sulfur content that needs of hydrocracking catalyst B.Then tetrabutylthiuram disulfide (TBTD) is mixed with heavy diesel fuel, this mixture is contained in the catalyst of elemental sulfur with the infusion process introducing, the TBTD consumption is 3% of a catalyst weight, and the heavy diesel fuel consumption is 20% of a catalyst weight.At normal pressure, not moving air and water vapor mixture atmosphere, handled 5 hours for 160 ℃ at last, obtain the outer pre-sulfide catalyst SCAT-B2 of device.
Comparative example 1
The outer pre-sulfide catalyst SCAT-C of device of preparation catalyst for hydrogenation de-waxing C (it is formed and character sees Table 4), process is as follows:
The elemental sulfur of fusing is introduced catalyst for hydrogenation de-waxing C, and the introducing amount of elemental sulfur is theoretical 120% of the sulfur content that needs of catalyst for hydrogenation de-waxing C.Then tetrabutylthiuram disulfide (TBTD) is mixed with heavy diesel fuel, this mixture introducing is contained in the catalyst of elemental sulfur, the TBTD consumption is 3% of a catalyst weight, and the heavy diesel fuel consumption is 20% of a catalyst weight.At normal pressure, not moving air and water vapor mixture atmosphere, handled 5 hours for 160 ℃ at last, obtain the outer pre-sulfide catalyst SCAT-C of device.
Composition and the character of table 2 Hydrobon catalyst A
| Form | |
| MoO 3/wt％ | 24.5 |
| NiO/wt％ | 4.6 |
| Aluminium oxide/wt% | Surplus |
| Character | |
| Pore volume/mlg -1 | 0.4 |
| Specific area/m 2·g -1 | 186 |
The composition of table 3 hydrocracking catalyst B (in the weight of catalyst) and character
| Composition/wt% | |
| WO 3 | 26.4 |
| NiO | 4.8 |
| Amorphous silicon aluminium (SiO 2Content 38wt%) | 34 |
| Modified Y molecular sieve (SiO 2/Al 2O 3Mol ratio 14) | 16 |
| γ-Al 2O 3 | Surplus |
| Character |
| Pore volume/mlg -1 | 0.42 |
| Specific area/m 2·g -1 | 248 |
Composition and the character of table 4 catalyst for hydrogenation de-waxing C
| Form | |
| NiO，wt％ | 1.8 |
| ZSM-5，wt％ | 85.0 |
| Aluminium oxide, wt% | Surplus |
| Character | |
| Specific surface, m 2/g | 320 |
| Pore volume, ml/g | 0.18 |
| The heap ratio, g/cm 3 | 0.68 |
Embodiment 11～16
Porous propping agent combination CA1～CA6 that embodiment 1～6 is obtained reactor of packing into of connecting with oxidation state catalyst for hydrogenation de-waxing C, porous propping agent combination CA1～CA6 is seated in the upper and lower of catalyst for hydrogenation de-waxing respectively, and the volume ratio of upper and lower filling porous propping agent combination is 1: 1.According to total sulfur content in the porous propping agent combination that is loaded is that the theory of oxidation state catalyst for hydrogenation de-waxing C needs 120% of sulfur content, loads porous propping agent combination and oxidation state catalyst for hydrogenation de-waxing C.With the hydrocracking tail oil is the evaluation test that raw material carries out on 200mL hydrogenation midget plant.After the catalyst filling finishes, using the nitrogen purge, draw hydrogen and set up the hydrogen circulation, when reactor inlet temperature is raised to 135 ℃, is 2h with the volume space velocity then
-1Introduce sulfurized oil catalyst is prewetted, activating catalyst under conditions of vulcanization treats that catalyst activates laggard feedstock oil, and the activation raw material sees Table 6, and activation condition sees Table 7.Feedstock oil character is as shown in table 5.Technological parameter and typical consequence see Table 8.
Comparative example 2
With the outer presulfurization catalyst for hydrogenation de-waxing SCAT-C of porous propping agent SA1 and the device filling of connecting, wherein porous propping agent is seated in the upper and lower of catalyst for hydrogenation de-waxing SCAT-C, filling ratio in upper and lower is 1: 1, and the admission space of SA1 and SCAT-C was than 1: 120.With the hydrocracking tail oil is the evaluation test that raw material carries out on 200mL hydrogenation midget plant.After the catalyst filling finishes, using the nitrogen purge, draw hydrogen and set up the hydrogen circulation, when reactor inlet temperature is raised to 135 ℃, is 2h with the volume space velocity then
-1Introduce sulfurized oil catalyst is prewetted, activating catalyst under conditions of vulcanization treats that catalyst activates laggard feedstock oil, and the activation raw material sees Table 6, and activation condition sees Table 7.Treat that catalyst activates laggard feedstock oil.Feedstock oil character is as shown in table 5.Technological parameter and typical consequence see Table 8.
Table 5 feedstock oil character
| Project | Density, g/cm -3 | Initial boiling point, ℃ | 50% distillates a little, ℃ | 90% distillates a little, ℃ | Condensation point, ℃ |
| Feedstock oil | 0.8359 | 306 | 421 | 485 | 27 |
Table 6 activation feedstock property
| Feedstock oil | Diesel oil A | Gasoline B |
| Density (20 ℃)/kgm -3 | 830.5 | 670.2 |
| The end point of distillation/℃ | 350 | 165 |
| Sulphur/μ gg -1 | 586 | 500 |
| Nitrogen/μ gg -1 | 118 | 100 |
The activation condition of table 7 embodiment and comparative example catalyst for hydrogenation de-waxing
| Embodiment | The activation raw material | Volume space velocity (h during pressure (MPa)/hydrogen to oil volume ratio/liquid -1) | Programming rate (℃/h) | The reactor inlet final temperature (℃) | Constant temperature time (h) | Beds maximum temperature rise during activation, ℃ |
| Embodiment 11 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 12 |
| Embodiment 12 | Diesel oil A | 6/500/3 | 30 | 300 | 12 | 13 |
| Embodiment 13 | Diesel oil A | 6/500/3 | 30 | 300 | 12 | 13 |
| Embodiment 14 | Diesel oil A | 15/1200/2 | 60 | 320 | 20 | 9 |
| Embodiment 15 | Gasoline B | 2/300/1 | 10 | 220 | 8 | 14 |
| Embodiment 16 | Diesel oil A | 8/800/2 | 50 | 280 | 18 | 12 |
| Comparative example 2 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 18 |
Table 8 technological parameter and typical consequence
Embodiment 17～22
With the outer presulfurization Hydrobon catalyst SCAT-A2 of device with after the Hydrobon catalyst A of oxidation state mixed in 65: 35 by volume, the filling of connecting with porous propping agent combination CA1～CA6 respectively again, wherein porous propping agent combination is seated in the upper and lower of Hydrobon catalyst, and filling ratio in upper and lower is 1: 1.The sulfur content that carries according to the hydrogenation catalyst SCAT-A2 of the sulfur content of the porous propping agent combination that is loaded and the outer presulfurization of device is theoretical 120% of the sulfur content that needs of hydrogenation catalyst, loads the mixture of porous propping agent combination and Hydrobon catalyst.With raw material I is the evaluation test that raw material carries out on 200mL hydrogenation midget plant.After the catalyst filling finishes, using the nitrogen purge, draw hydrogen and set up the hydrogen circulation, when reactor inlet temperature is raised to 135 ℃, is 2h with the volume space velocity then
-1Introduce sulfurized oil catalyst is prewetted, activating catalyst under conditions of vulcanization treats that catalyst activates laggard feedstock oil, and the activation raw material sees Table 6, and activation condition sees Table 9.Treat that catalyst activates laggard feedstock oil.Feedstock oil character is as shown in table 10.Technological parameter and typical consequence see Table 11.
Comparative example 3
With the outer presulfurization Hydrobon catalyst SCAT-A1 of porous propping agent SA1 and the device filling of connecting, wherein porous propping agent is seated in the upper and lower of Hydrobon catalyst SCAT-A1, filling ratio in upper and lower is 1: 1, and the admission space of SA1 and SCAT-A1 was than 1: 120.With raw material I is the evaluation test that raw material carries out on 200mL hydrogenation midget plant.After the catalyst filling finishes, using the nitrogen purge, draw hydrogen and set up the hydrogen circulation, when reactor inlet temperature is raised to 135 ℃, is 2h with the volume space velocity then
-1Introduce sulfurized oil catalyst is prewetted, activating catalyst under conditions of vulcanization treats that catalyst activates laggard feedstock oil, and the activation raw material sees Table 6, and activation condition sees Table 9.Treat that catalyst activates laggard feedstock oil.Feedstock oil character is as shown in table 10.Technological parameter and typical consequence see Table 11.
Embodiment 23～28
With the outer presulfurization Hydrobon catalyst SCAT-A2 of device and the outer presulfurization hydrocracking catalyst SCAT-B1 of device and the porous propping agent combination CA1～CA6 filling of connecting respectively, wherein the outer presulfurization Hydrobon catalyst SCAT-A2 of device is seated in the upper strata of the outer presulfurization hydrocracking catalyst SCAT-B1 of device, porous propping agent combination is seated in the upper strata of the outer presulfurization Hydrobon catalyst SCAT-A2 of device and the lower floor of the outer presulfurization hydrocracking catalyst SCAT-B1 of device, and the filling ratio of porous propping agent combination in the upper and lower is 1: 1.The admission space ratio of outer presulfurization Hydrobon catalyst SCAT-A2 of device and the outer presulfurization hydrocracking catalyst of device is 1: 1.2.The sulfur content that carries according to the hydrocracking catalyst SCAT-B1 of the sulfur content of the porous propping agent combination that is loaded and outer presulfurization Hydrobon catalyst SCAT-A2 of device and the outer presulfurization of device is theoretical 120% of the sulfur content that needs of Hydrobon catalyst A and hydrocracking catalyst B, loads porous propping agent combination and hydrocracking catalyst.With the raw material II is the evaluation test that raw material carries out on 200mL hydrogenation midget plant.After the catalyst filling finishes, using the nitrogen purge, draw hydrogen and set up the hydrogen circulation, when reactor inlet temperature is raised to 135 ℃, is 2h with the volume space velocity then
-1Introduce sulfurized oil catalyst is prewetted, activating catalyst under conditions of vulcanization treats that catalyst activates laggard feedstock oil, and the activation raw material sees Table 6, and activation condition sees Table 12.Treat that catalyst activates laggard feedstock oil.Feedstock oil character is as shown in table 10.Vacuum distillate hydrocracking section parameter and typical consequence see Table 13.
Comparative example 4
With the outer presulfurization Hydrobon catalyst SCAT-A1 of porous propping agent SA1 and device and the outer presulfurization hydrocracking catalyst SCAT-B2 of the device filling of connecting, wherein the outer presulfurization Hydrobon catalyst SCAT-A1 of device is seated in the upper strata with the outer presulfurization hydrocracking catalyst SCAT-B2 of device, porous propping agent SA1 be seated in the outer presulfurization Hydrobon catalyst SCAT-A1 upper strata of device and and the lower floor of the outer presulfurization hydrocracking catalyst SCAT-B2 of device, the filling ratio of porous propping agent in the upper and lower is 1: 1, and SA1 is 1: 120 with the ratio of SCAT-A1 and SCAT-B2 filling cumulative volume.With the raw material II is the evaluation test that raw material carries out on 200mL hydrogenation midget plant.After the catalyst filling finishes, using the nitrogen purge, draw hydrogen and set up the hydrogen circulation, when reactor inlet temperature is raised to 135 ℃, is 2h with the volume space velocity then
-1Introduce sulfurized oil catalyst is prewetted, activating catalyst under conditions of vulcanization treats that catalyst activates laggard feedstock oil, and the activation raw material sees Table 6, and activation condition sees Table 12.Treat that catalyst activates laggard feedstock oil.Feedstock oil character is as shown in table 10.Vacuum distillate hydrocracking section parameter and typical consequence see Table 13.
The activation condition of table 9 embodiment and comparative example Hydrobon catalyst
| Embodiment | The activation raw material | Volume space velocity (h during pressure (MPa)/hydrogen to oil volume ratio/liquid -1) | Programming rate (℃/h) | The reactor inlet final temperature (℃) | Constant temperature time (h) | Beds maximum temperature rise during activation, ℃ |
| Embodiment 17 | Diesel oil A | 4/800/2 | 30 | 320 | 12 | 14 |
| Embodiment 18 | Diesel oil A | 6/500/2 | 30 | 300 | 12 | 13 |
| Embodiment 19 | Diesel oil A | 6/500/2 | 30 | 300 | 12 | 12 |
| Embodiment 20 | Diesel oil A | 15/1200/2 | 60 | 320 | 20 | 9 |
| Embodiment 21 | Gasoline B | 4/300/21 | 20 | 320 | 8 | 15 |
| Embodiment 22 | Diesel oil A | 8/800/2 | 50 | 300 | 18 | 12 |
| Comparative example 3 | Diesel oil A | 4/800/2 | 30 | 300 | 12 | 25 |
Table 10 feedstock oil main character
| The oil product title | Raw material I (urging bavin) | Raw material II (vacuum distillate) |
| Density (20 ℃)/gcm -3 | 0.88951 | 0.9125 |
| The boiling range scope/℃ | 162-356 | 335-532 |
| Sulphur/μ g.g -1 | 23000 | - |
| Nitrogen/μ g.g -1 | 8421 | - |
| The BMCI value | - | 44 |
Table 11 diesel oil hydrofining technological parameter and typical consequence
The activation condition of table 12 embodiment and the supporting catalyst of comparative example hydrocracking
| Embodiment | The activation raw material | Volume space velocity (h during pressure (MPa)/hydrogen to oil volume ratio/total liquid -1) | Programming rate (℃/h) | The final intensification (℃) | Constant temperature time (h) | Beds maximum temperature rise during activation, ℃ |
| Embodiment 23 | Diesel oil A | 15/800/2 | 30 | 360 | 22 | 12 |
| Embodiment 24 | Diesel oil A | 8/500/3 | 30 | 340 | 22 | 13 |
| Embodiment 25 | Diesel oil A | 8/500/3 | 50 | 340 | 22 | 14 |
| Embodiment 26 | Diesel oil A | 15/1200/2 | 40 | 320 | 20 | 9 |
| Embodiment 27 | Gasoline B | 8/1300/1 | 15 | 320 | 18 | 14 |
| Embodiment 28 | Diesel oil A | 8/800/2 | 30 | 360 | 22 | 12 |
| Comparative example 4 | Diesel oil A | 8/800/2 | 30 | 360 | 22 | 18 |
Table 13 vacuum distillate hydrocracking section parameter and typical consequence
Annotate: among the present invention, wt% is a mass fraction, and v% is that body is counted mark.
Claims (21)
1. the activation method of a hydrogenation catalyst comprises
(A) respectively porous propping agent combination and hydrogenation catalyst are packed in the reactor;
(B) activation hydrogenation catalyst;
The porous propping agent combination described in the step (A) wherein, its composition comprises following component:
(1) porous propping agent;
(2) sulphur in element sulphur, accounts for 20%～300% of porous propping agent weight;
(3) organic solvent accounts for 0～50% of porous propping agent weight;
(4) auxiliary agent accounts for 0～25% of porous propping agent weight.
2. according to the described activation method of claim 1, it is characterized in that the sulfur content of described porous propping agent combination is enough to make the full cure of oxidation state hydrogenation catalyst, then hydrogenation catalyst all adopts the hydrogenation catalyst of oxidation state; Described full cure is meant that the sulfur content of porous propping agent combination is theoretical 80%～200% of the sulfur content that needs of hydrogenation active metals in porous propping agent combination and the hydrogenation catalyst.
3. according to the described activation method of claim 2, it is characterized in that described " full cure " is meant that the sulfur content of porous propping agent combination is theoretical 85%～120% of the sulfur content that needs of hydrogenation active metals in porous propping agent combination and the hydrogenation catalyst.
4. according to the described activation method of claim 1, the sulfur content deficiency that it is characterized in that described porous propping agent combination is so that under the situation of oxidation state hydrogenation catalyst full cure, described hydrogenation catalyst adopts the hydrogenation catalyst of the outer presulfurization of device, and the hydrogenation catalyst of the outer presulfurization of device and the total sulfur content that porous propping agent combination provides make the hydrogenation catalyst full cure; Described full cure is meant that the hydrogenation catalyst of the outer presulfurization of device and total sulfur content that carries of porous propping agent combination are theoretical 80%～200% of the sulfur contents that needs of hydrogenation active metals in porous propping agent combination and the hydrogenation catalyst.
5. according to the described activation method of claim 4, it is characterized in that described " full cure " is meant that the hydrogenation catalyst of the outer presulfurization of device and total sulfur content that carries of porous propping agent combination are theoretical 85%～120% of the sulfur contents that needs of hydrogenation active metals in porous propping agent combination and the hydrogenation catalyst.
6. according to the described activation method of claim 4, it is characterized in that described hydrogenation catalyst all adopts the hydrogenation catalyst of the outer presulfurization of device.
7. according to the described activation method of claim 4, it is characterized in that described hydrogenation catalyst partly adopts the hydrogenation catalyst of the outer presulfurization of device, part adopts the hydrogenation catalyst of oxidation state, both mixed packings or layering filling.
8. according to the described activation method of claim 1, it is characterized in that the porous propping agent combination described in the step (A), comprise following component:
(1) porous propping agent;
(2) sulphur in element sulphur, accounts for 50%～280% of porous propping agent weight;
(3) organic solvent accounts for 0%～30% of porous propping agent weight;
(4) auxiliary agent accounts for 0.5%～25.0% of porous propping agent weight.
9. according to the described activation method of claim 1, it is characterized in that the described activation hydrogenation catalyst of step (B) adopts the wet method sulfuration, comprise nitrogen replacement, draw hydrogen and set up hydrogen circulation, introduce that sulfurized oil is prewetted to catalyst and the sulfuration of catalyst that wherein used sulfurized oil is one or more in gasoline, kerosene and the diesel oil; Sulfurized oil is introduced reactor carry out catalyst when prewetting, the control reactor inlet temperature is 130～160 ℃, volume space velocity 0.2～20h
-1Following condition is adopted in the sulfuration of described catalyst: pressure 1～20MPa, H
2Air speed is 100～10000h
-1, 5～60 ℃/h of programming rate, the reactor inlet final temperature is 200 ℃～400 ℃, and under this temperature constant temperature 2～36 hours.
10. according to the described activation method of claim 9, when it is characterized in that the sulfuration of described catalyst, the reactor inlet final temperature is 280～360 ℃.
11. according to the described activation method of claim 1, it is characterized in that porous propping agent combination is seated in the upstream of hydrogenation catalyst in the step (A), perhaps porous propping agent combination be seated in simultaneously the upstream and downstream of hydrogenation catalyst.
12., it is characterized in that described porous propping agent is the active porous proppant that does not contain the inertia porous propping agent of reactive metal and/or contain a small amount of reactive metal according to the described activation method of claim 1.
13., it is characterized in that the content of reactive metal in the described active porous proppant accounts for below 2.0% of porous propping agent weight in oxide according to the described activation method of claim 12.
14. according to the described activation method of claim 12, it is characterized in that described inertia porous propping agent is one or more in aluminium oxide, silica, titanium oxide, zirconia, the zinc oxide, described active porous proppant is a supported active metal on one or more in aluminium oxide, silica, titanium oxide, zirconia, zinc oxide; Described reactive metal is one or more in VIB and/or the group VIII metal.
15., it is characterized in that sulphur in the described porous propping agent combination comes from one or more in elemental sulfur, inorganic sulphide and the organic sulfur compound according to the described activation method of claim 1.
16., it is characterized in that described sulphur comes from elemental sulfur according to claim 1 or 9 described activation methods.
17., it is characterized in that the auxiliary agent in the described porous propping agent combination is the thiurams material according to the described activation method of claim 1.
18., it is characterized in that described thiurams material is one or more in tetrabutylthiuram disulfide, tetra-benzyl thiram disulfide, DMDPTD dimethyl diphenylthiuram disulfide, tetraethylthiuram disulfide, DMDPTD dimethyl diphenylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, diethyl diphenyl thiuram disulfide and the tetramethylthiuram disulfide according to the described activation method of claim 17.
19., it is characterized in that described organic solvent is one or more in hydrocarbon ils and the organic carboxylic ester according to the described activation method of claim 1.
20. in accordance with the method for claim 19, it is characterized in that described hydrocarbon ils from naphtha, gasoline, kerosene, diesel oil, white oil, lam-oil, lube base oil, straight run heavy distillate and the decompression heavy distillate one or more, organic carboxylic ester is the organic carboxylic ester that contains 6～60 carbon atoms.
21., it is characterized in that described hydrogenation catalyst comprises one or more in Hydrobon catalyst, hydrocracking catalyst and the catalyst for hydro-upgrading according to the described activation method of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0224462A2 (en) * | 1985-10-24 | 1987-06-03 | Monsanto Company | Carriers for catalysts |
| CN1861257A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Treatment method before application of hydrogenation catalyst |
| CN1861258A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Sulfurized type catalyst, and its prepn. method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0224462A2 (en) * | 1985-10-24 | 1987-06-03 | Monsanto Company | Carriers for catalysts |
| CN1861257A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Treatment method before application of hydrogenation catalyst |
| CN1861258A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Sulfurized type catalyst, and its prepn. method |
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