CN101417247A - Porous propping agent combination and preparation method thereof - Google Patents
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Abstract
The invention discloses a porous propping agent combination and a preparation method thereof; the propping combination comprises a porous propping agent, sulfur which occupies 20-300 percent of the weight of the porous propping agent, organic solvent which occupies 0-50 percent of the weight of the porous propping agent and auxiliary agent which occupies 0-25.0 percent of the weight of the porous propping agent. The propping agent combination is suitable for hydrogenation disposal process. The porous propping agent combination provides vulcanizing agent for the oxidated hydrogenation catalyst, shortens the commencement time of the device, improves the production efficiency, overcomes the defects of pre-vulcanization in the device, and can solve the problem of concentrative heat discharge of pre-vulcanized catalyst outside the device. Furthermore, the sulfur introduced in the porous propping agent is mainly arranged in holes of the propping agent, increases no volume of the propping agent, thus affecting no disposal quantity of the device further.
Description
Technical field
The present invention relates to a kind of porous propping agent combination and preparation method thereof, especially for porous propping agent combination of hydrotreatment process and preparation method thereof.
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.Yet the effect and the catalytic performance of presulfurization are in close relations, and the method for presulfurization and process control are all very important.
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, 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 tungsten-nickel series hydrogenating catalyst for refining layering in catalyst: the vulcanizing agent weight ratio is the ratio of the 4:1～20:1 tungsten-nickel hydrogenation reactor of packing into jointly, joins the hydrogen presulfurization with nitrogen do carrier gas then.Above-mentioned two patented methods, all be that solid sulfurizing agent is seated in separately on the hydrogenation catalyst bed, these vulcanizing agents account for bigger space in hydrogenation reactor, this not only influences the treating capacity of device, and in sulfidation, need to carry out the married operation of nitrogen and hydrogen, in practical operation, have certain degree of difficulty.
Before the outer presulfurization of catalyst device was meant filling, catalyst had cured or vulcanizing agent exists, and need not to introduce the method for vulcanizing agent after being loaded in the reactor.The outer presulfurization cure time of device is short, 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, part 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, these heats can make beds produce bigger temperature rise, thereby make the difficult control of activation process of catalyst.
Hydrogenation reactors such as hydrofinishing, hydrocracking, hydrotreatment are 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, all is to carry out presulfurization at the hydrogenation catalyst that contains reactive metal according to existing method for pre-sulphuration, and this class proppant does not need sulfuration.
Summary of the invention
The invention provides a kind of porous propping agent combination and preparation method thereof.This porous propping agent combination has in use not only kept its original character, but also can provide vulcanizing agent in hydrogenation catalyst activation process, the curtailment of operation, enhances productivity.
Porous propping agent combination of the present invention, 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 0.5%～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%.
Described porous propping agent is the inertia porous propping agent, does not contain reactive metal.Described proppant be in the porous refractory inorganic oxides such as aluminium oxide, silica, titanium oxide, zirconia, zinc oxide one or more.
Used vulcanizing agent when the sulphur in the described porous propping agent combination can come from the outer presulfurization hydrogenation catalyst of existing preparing device can be in elemental sulfur, inorganic sulfocompound and the sulfur-containing organic compound one or more, preferably adopts elemental sulfur.Wherein inorganic sulfocompound can be carbon disulfide, and sulfur-containing organic compound can be selected from the organic polysulfide described in mercaptan, thioether, disulphide and the CN1611577A.
Also contain auxiliary agent 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%, 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.
Organic solvent wherein 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% 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 proppant 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.
Auxiliary agent among the present invention and organic solvent and other other additive can adopt infusion process to introduce in the 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 with infusion process 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%.
Porous propping agent combination of the present invention is applicable in the hydrotreatment process.
In the porous propping agent combination of the present invention, porous propping agent itself does not need sulfuration, but provide vulcanizing agent for the oxidation state hydrogenation catalyst, can shorten the on-stream time of device, enhance productivity, overcome the shortcoming of presulfurization in the device, but also can concentrate the problem of heat release by the outer pre-sulfide catalyst of resolver, the heat that makes vulcanizing agent and hydrogen reaction is mainly in the proppant part, and the heat that the reactive metal sulfuration generates is mainly in the hydrogenation catalyst part.
In addition, generally speaking, at the top of hydrogenation plant or top and bottom to load conventional porous propping agent, at this moment adopt porous propping agent combination of the present invention to replace conventional porous propping agent, because porous propping agent combination of the present invention is that sulphur is incorporated in the duct of porous propping agent, therefore, can not increase the volume of porous propping agent, thereby can not influence the treating capacity of device, after the activating catalyst, still keep the original effect of porous propping agent simultaneously.
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, not only avoid concentrating heat release, and help the hydrogenation catalyst full cure.
The specific embodiment
Below in conjunction with embodiment porous propping agent combination of the present invention and effect are described further, but do not limit protection scope of the present 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, 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 catalyst 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 (mixture of peanut oil and heavy diesel fuel weight ratio 4:1), 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 normal pressure, water vapour and volume of air than 5:1 atmosphere under, 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 the mixture of n-butyl acetate, heavy diesel fuel weight ratio 2:6, its consumption is 6% of a porous propping agent weight, obtains porous propping agent combination CA6.
Comparative example 1
The outer pre-sulfide catalyst of device of preparation catalyst for hydrogenation de-waxing A (it is formed and character sees Table 2), process is as follows:
The elemental sulfur of fusing is introduced catalyst for hydrogenation de-waxing A, and the introducing amount of elemental sulfur is theoretical 120% of the sulfur content that needs of catalyst for hydrogenation de-waxing A.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 B of device.
Embodiment 7～12
Porous propping agent combination CA1～CA6 that embodiment 1～6 is obtained filling of connecting with oxidation state catalyst for hydrogenation de-waxing A respectively, wherein porous propping agent combination is seated in the upper and lower of catalyst for hydrogenation de-waxing respectively, 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 A needs 120% of sulfur content, loads porous propping agent combination and oxidation state catalyst for hydrogenation de-waxing A.After the catalyst filling finishes, at first activate under hydrogen atmosphere, the activation raw material sees Table 4, and activation condition sees Table 5.With the hydrocracking tail oil is that raw material (feedstock oil character is as shown in table 3) carries out the Hydrodewaxing reaction on the fixed bed hydrogenation device, and the technological parameter and the typical consequence of operation see Table 6.
Comparative example 2
With the porous propping agent SA1 and the filling of connecting with the outer presulfurization catalyst for hydrogenation de-waxing B of device, wherein porous propping agent is seated in the upper and lower of catalyst for hydrogenation de-waxing B, and filling ratio in upper and lower is 1:1, and SA1 compares 1:120 with the admission space of catalyst B.After the catalyst filling finishes, at first activate under hydrogen atmosphere, the activation raw material sees Table 4, and activation condition sees Table 5.With the hydrocracking tail oil is that raw material (feedstock oil character is as shown in table 3) carries out the Hydrodewaxing reaction on the fixed bed hydrogenation device, and the technological parameter and the typical consequence of operation see Table 6.
Composition and the character of table 2 catalyst for hydrogenation de-waxing A
| 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 |
Table 3 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 4 activation feedstock property
| Feedstock oil | Diesel oil A |
| Density (20 ℃)/kgm -3 | 830.5 |
| The end point of distillation/℃ | 350 |
| Sulphur/μ gg -1 | 586 |
| Nitrogen/μ gg -1 | 118 |
The activation condition of table 5 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 final intensification (℃) | Constant temperature time (h) | Beds maximum temperature rise during activation, ℃ |
| Embodiment 7 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 12 |
| Embodiment 8 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 9 |
| Embodiment 9 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 11 |
| Embodiment 10 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 11 |
| Embodiment 11 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 10 |
| Embodiment 12 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 9 |
| Comparative example 2 | Diesel oil A | 4/800/2 | 30 | 280 | 12 | 18 |
Table 6 technological parameter and typical consequence
Claims (15)
1, a kind of porous propping agent combination, its composition comprises following component:
(1) inertia 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 0～25.0% of porous propping agent weight.
2,, it is characterized in that described sulphur accounts for 50%～280% of porous propping agent weight according to the described porous propping agent combination of claim 1.
3, according to the described porous propping agent combination of claim 1, it is characterized in that described organic solvent, account for porous propping agent weight 0.5%～30%.
4,, it is characterized in that described auxiliary agent accounts for porous propping agent weight 2.0%～10.0% according to the described porous propping agent combination of claim 1.
5, according to the described porous propping agent combination of claim 1, it is characterized in that described porous propping agent be in the porous refractory inorganic oxides such as aluminium oxide, silica, titanium oxide, zirconia, zinc oxide one or more.
6,, it is characterized in that sulphur in the described porous propping agent comes from one or more in elemental sulfur, inorganic sulfocompound and the sulfur-containing organic compound according to the described porous propping agent combination of claim 1.
7,, it is characterized in that described sulphur comes from elemental sulfur according to the described porous propping agent combination of claim 1; Described auxiliary agent is the thiurams material.
8,, 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 porous propping agent combination of claim 7.
9,, it is characterized in that described organic solvent is one or more in hydrocarbon ils and the organic carboxylic ester according to the described porous propping agent combination of claim 1.
10, according to the described porous propping agent combination of claim 9, it is characterized in that described hydrocarbon ils from the heavy end wet goods of naphtha, gasoline, kerosene, diesel oil, white oil, lam-oil, lube base oil, straight run and decompression one or more, organic carboxylic ester is the organic carboxylic ester that contains 6～60 carbon atoms.
11, the preparation method of the arbitrary described porous propping agent combination of claim 1～10 comprises the steps:
(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.
12, according to the described preparation method of claim 11, the mode in the described sulphur introducing proppant that it is characterized in that is selected according to the type of vulcanizing agent, when using elemental sulfur to make vulcanizing agent, adopt distillation absorption, fusing dipping or be dispersed in the organic solution and flood, adopt other vulcanizing agent except that elemental sulfur to adopt infusion process to introduce.
13, according to the described preparation method of claim 11, it is characterized in that auxiliary agent in the step (2), one of the select progressively of organic solvent and vulcanizing agent introducing hydrogenation catalyst is following: (1) introduces auxiliary agent earlier, 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 mixes introducing simultaneously.
14,, it is characterized in that described auxiliary agent thiurams material is to introduce in the proppant after it is dissolved in solvent, removes with the method for evaporation then and desolvates according to the described preparation method of claim 11; Described solvent is one or more in benzene, acetone and the chloroform.
15, according to the described preparation method of claim 11, it is characterized in that describedly after introducing auxiliary agent, vulcanizing agent and organic solvent, carrying out heat treated, condition is 50～300 ℃ and handled 1～40 hour down; Heat treated atmosphere is that inert gas, oxygen content are in carrier of oxygen and the water vapour one or more of having of 0.1v%～30v%.
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| CN105753052A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院大连化学物理研究所 | Synthesis method of supported MoS2 catalyst |
| CN109174165A (en) * | 2018-08-07 | 2019-01-11 | 黑龙江莱睿普思环境科技发展有限公司 | For the catalyst and preparation method thereof in waste mineral oil plus hydrogen regeneration technology |
| CN109913197A (en) * | 2019-03-21 | 2019-06-21 | 中国石油天然气股份有限公司 | A kind of displacement of reservoir oil proppant and preparation method thereof |
| CN109943315A (en) * | 2019-03-21 | 2019-06-28 | 中国石油天然气股份有限公司 | A kind of scale inhibition proppant and preparation method thereof |
| CN109913197B (en) * | 2019-03-21 | 2021-03-09 | 中国石油天然气股份有限公司 | Oil displacement proppant and preparation method thereof |
| CN109943315B (en) * | 2019-03-21 | 2021-09-28 | 中国石油天然气股份有限公司 | Scale inhibition proppant and preparation method thereof |
| CN116478679A (en) * | 2023-04-24 | 2023-07-25 | 西南石油大学 | Propping agent and preparation method thereof |
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