CN1632070A - Hydrogenation catalyst aid for residual oil suspended bed and its use - Google Patents
Hydrogenation catalyst aid for residual oil suspended bed and its use Download PDFInfo
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Abstract
Disclosed is a suspended bed hydrogenation catalyst assistant belongs to the fields of oil procession and oil chemical technology. The assistant contains are or the combination of several ones willingly chosen from high molecule, synthesis organic high molecule, natural surface active agent, synthesis surface active agent, condensed aromatics, organic alcohol, organic carboxylate surfactant, organic carboxylic acid amide, organic carboxylic acid halogen, organic phosphide. It can be applied in the course of suspended bed hydrogenation, as well as that of hydrogenation mixing of hydrogenation and liquidifying coal. By adding the assistant, the hydrogenation effect of catalyst can be increased, as well as decreasing scale formation in reactor in the time of decreasing scale formation in fractional distillation part of the reacting pipe.
Description
Technical field:
The present invention relates to a kind of catalyst aid in the hydrogenation of residual oil suspended bed process, belong to refining of petroleum and petrochemical technology field.This auxiliary agent can be applied to the hydrogenation of residual oil suspended bed process, also can be applied to residual oil and coal, residual oil and plastic waste, residual oil and waste rubber, plastic waste and waste rubber hydrogenation refines and the coal liquefaction process altogether, add the hydrogenation that this catalyst aid helps to improve catalyzer and press down burnt effect, the more important thing is the reactor coking amount that helps suppressing in the said process, reduce at furnace tubing defeated coking and the scale formation that reaches positions such as fractionation of reaction tubes simultaneously.
Background technology:
Along with the heaviness day by day of crude oil extraction and market to the continuous increase of light-end products demand, people's counterweight, residual oil lighting technology requirement are grown to even greater heights.In numerous residual oil complete processings, dreg-oil suspension bed hydrogenation cracking technology comes into one's own day by day, suspension bed residual oil hydrogenation is to allow residual oil under the condition of hydrogen and hydrogenation catalyst existence thermo-cracking and hydrogenation reaction take place, thereby can have the characteristics of hot-work and two kinds of technologies of hydrogenation concurrently.Because numerous advantages such as it has the transformation efficiency height, flow process is simple, facility investment is few, diesel yield is high and coking yield is low, thereby application prospect is very wide.
Existing dreg-oil suspension bed catalyzer mainly contains:
(1) add the technology of solid particle catalyst, as the floating bed hydrogenation technology of early stage early 1950s Germany, this technology is used for coal tar hydrogenating with the ferrous sulfate load on brown coal, but its hydrogenation activity is very low.The combination cracking process (VCC) that German afterwards VEBA company develops on the basis of coal and coal tar hydrogenating technology is a kind of thermal cracking processes of high conversion, brown coal and the levigate back of coke as additive form slurry oil with residual oil raw material, add preheating together behind new hydrogen and the circulation gas, the upper reaches enters Liquid-phase reactor, under the pressure of 440～485 ℃ and 25MPa, transform with One-through design.Reaction product is drained after separating and is accounted for residue combined feed total feed massfraction about 6%, that contain solid 50%.The seventies, at the needs of oil sands bitumen upgrading, Canadian mineral products and energy technology center begin to develop the CHANMET hydrocracking process, and have carried out amplification test in 1985 at Canadian Montreal refinery.The principal feature of this technology is to adopt ferrous sulfate and coal dust to grind the back as additive, and the massfraction of addition is about 1%～3%.The stock oil of mixed additive and recycle hydrogen are being heated to temperature of reaction respectively in the process furnace separately.For preventing that oil from tube coking, injecting small amount of recycled hydrogen in the stove import.Be heated to the oil of temperature of reaction and hydrogen injecting reactor bottom, at 435～455 ℃ with approximately carry out the reaction mass transformation efficiency under the 14MPa and can reach 90%.CAMNET thinks the FeSO that is loaded with about granularity 100 orders
4Coal dust be added in the residual oil as scorch retarder, can reduce the formation of coke and green coke precursor significantly.They also use the flue dust of fire coal or oil fired power plant as scorch retarder, the add-on massfraction is 1% in residual oil, at 10.3MPa, 450 ℃ of following hydrogenation, when 524 ℃+transformation efficiency is 51.7%, desulfurization degree is 31.5% o'clock, and coking yield has obvious minimizing than the blank sample.The researchist at Canada mineral products and energy technology center also think particle diameter less than 60 purpose coal dusts, carry last Fe, Co, metal-salts such as Mo, Zn more than 10% after, the scorch retarder effect as floating bed hydrocracking under 1.4～24MPa pressure is fine.
PetroCanada proposed to be used for petroleum coke powder and ferric sulfate scorch retarder the floating bed hydrogenation of residual oil in 1991 again.They will be crushed to the broken coke button of 8～16 purposes and ferric sulfate, heavy oil mixes, and three's ratio is 35: 15: 50, and the grinding machine of scoring then is milled to molysite and coke powder particle all less than 200 orders, and is most of less than 30um.This scorch retarder is used to subtract the slag floating bed hydrogenation, and as reaction pressure 13.9MPa, pitch transformation efficiency during 450 ℃ of temperature (basic noncoking) can reach 88%, and equal conditions during down with coal tar-ferrous sulfate scorch retarder the bituminous transformation efficiency have only 75%.The HDH process of Venezuela INTEVEP company research and development is made catalyzer with the natural mineral fine powder that contains Ni and V, and residual oil is carried out hydro-upgrading.Technological process and aforementioned floating bed hydrogenation are similar, and typical operation conditions is: 420～470 ℃ of temperature of reaction, reaction pressure 7～14MPa, air speed 0.3～1.0h
-1, vapour-liquid ratio is 1000～5000Nm
3/ m
3, catalyzer add-on massfraction 2%～5%.One way is 85%～90% by 500 ℃ of transformation efficiencys when processing different raw materials, and coke yield is 1.3%～2.3%, and the gaseous mass productive rate is 9.8%～10.2%.Reaction product is told product liquid through heat separator, and the heat branch bottoms that contains used catalyst enters the catalyst separating system.Unconverted tail oil and catalyst separating, the spent catalyst drying of telling are burned the back and are got rid of.
(2) homogeneous catalyst comprises oil soluble organo-metallic catalyst and water-soluble catalyst, and these two kinds of catalyzer all are that the form with metal particle and sulfide thereof exists in reaction process, therefore is not the homogeneous catalyst on the colloid chemistry meaning.Carry out hydrogenation of residual oil suspended bed with Canadian (HC) with the oil soluble metal catalyzer
3Technology is representative.The water-soluble catalyst suspension bed residual oil hydrogenation then has Exxon company to make the technology of catalyzer with phospho-molybdic acid, and Chevron company makes the technology of catalyzer etc. with ammonium molybdate.
(3) catalyzer of composite type, for example IFP is composite with molybdenum naphthenate and cobalt naphthenate, the ferric oxide of Exxon company and the composite suspension bed residual oil hydrogenation that is used for of phenol cyanines cobalt, it is 7% that the latter works as the ferric oxide massfraction, the cobalt consumption is 400 μ gg
-1The time, 6.8% the when coking yield under the same reaction conditions can be from no scorch retarder reduces to 0.4%.Except various oil soluble metal compounds are directly used in the suspension bed, also has the method that itself and various pressed powder are used.Exxon company adds the molybdenum naphthenate of 350～500 μ g/g (in metal) and the brown iron oxide that massfraction is about 1% (in iron) in the seventies in resid feed, after the prevulcanized at 438 ℃, hydrogenation under the 13.7MPa, the green coke amount is substantially below 0.5%.And catalyzer can leach repeatedly and use.The normal back of circulation only needs to mend about 1/6 raw catalyst.They proposed again afterwards with molybdenum naphthenate load catalyzer as floating bed hydrogenation on powder of stainless steel.
Nobum itum Ohtabe has then proposed molybdenum naphthenate or other ultrafine solids particulates added in the residual oil together and has stirred evenly, and carries out hydrocracking.When organic acid metal salt consumption is 300～1000 μ g/g, ultrafine solids particulate add-on massfraction is 2%～10% o'clock, and 520 ℃ of transformation efficiencys can reach 70%～80%.
Exxon company also once used CrO
3With the alcohol reaction, get oil soluble di-t-butyl chromic salt, this catalyzer is used for the floating bed hydrogenation that heavy Arab subtracts slag, in 14.4MPa, 443 ℃ of reactions down, when the catalyzer add-on was 350 μ g/g, 524 ℃+transformation efficiency was 84.6%, coking yield is 1.43%
No matter adopt which kind of catalyzer, because hydrogenation of residual oil suspended bed technology is to carry out under 430～470 ℃ of high temperature, residual oil green coke phenomenon is more serious, especially under the high temperature in the continuous operation reactor coking phenomenon serious, this problem affects the process of industrialization of this technology always.And in order to prolong the continuous firing cycle, reduce under the high temperature that the reactor coking becomes the focus that addresses this problem undoubtedly in the continuous operation.
Summary of the invention:
The objective of the invention is to develop a kind of catalyst adjuvant of hydrogenation of residual oil suspended bed, add a small amount of this auxiliary agent, can play the hydrogenation that improves the hydrogenation of residual oil suspended bed catalyzer on the one hand and press down burnt effect, on the other hand and the more important thing is and can reduce the hydrogenation of residual oil suspended bed reactor coking phenomenon in the continuous operation at high temperature, thus prolong the on-stream time of hydrogenation of residual oil suspended bed device greatly.
The object of the present invention is achieved like this, at the hydrogenation of residual oil suspended bed process, develop a kind of hydrogenation of residual oil suspended bed catalyst adjuvant, it is characterized in that this auxiliary agent contains any one material or any two kinds or any two or more composition in natural organic high-molecular, synthetic organic polymer, natural surface active agent, synthetic surfactant, condensed-nuclei aromatics, organic alcohol, organic carboxyl acid, organic carboxylate, organic carboxyl acid acid amides, organic carboxyl acid carboxylic acid halides, the Organophosphorous compounds, its addition is 10～8000 μ g/g of residual oil raw material.
This catalyst adjuvant not only can be applied to the hydrogenation of residual oil suspended bed process, also can be applied to residual oil and coal, residual oil and plastic waste, residual oil and waste rubber, plastic waste and waste rubber hydrogenation and refine process and coal liquefaction process altogether.This auxiliary agent can play the hydrogenation that improves hydrogenation catalyst and press down burnt effect, reduces the hydrogenator coking amount in the continuous operation at high temperature, reduces the fouling at position such as, fractionation defeated at reaction tubes simultaneously, thereby prolongs the on-stream time of hydrogenation unit greatly.
Embodiment:
Describe the present invention in detail below in conjunction with embodiment.
The present invention be directed to the hydrogenation of residual oil suspended bed process, develop a kind of hydrogenation catalyst agent aid, it contains a kind of or any two kinds or two or more combination arbitrarily in the following material: natural organic high-molecular, synthetic organic polymer, natural surface active agent, synthetic surfactant, condensed-nuclei aromatics, organic alcohol, organic carboxyl acid, organic carboxylate, organic carboxyl acid acid amides, organic carboxyl acid carboxylic acid halides, Organophosphorous compounds, its addition are 10～8000 μ g/g of residual oil raw material.Natural organic high-molecular or synthetic organic polymer are native starch, Mierocrystalline cellulose, polyoxyethylene glycol, terephthalic acid ethylene glycol polycondensate, terephthalic acid quadrol polycondensate and other di-carboxylic acid ethylene glycol polycondensate and other di-carboxylic acid diamine polycondensate, comprise the above modifier natural or synthetic polymer simultaneously, polyacrylamide, polyacrylonitrile, partially hydrolyzed polyacrylamide, resol and their derivative also comprise polyethylene, polypropylene, polystyrene and their modifier and derivative.The molecular weight ranges of described natural organic high-molecular or synthetic organic polymer is 100～20000000.Described tensio-active agent comprises aniorfic surfactant, cationic surfactant, nonionogenic tenside, positively charged ion-nonionic amphoterics, negatively charged ion-nonionic amphoterics.Described anion surfactant refers to alkyl benzene sulphonate (ABS) series, alkylbenzene sulfonate series, alkyl naphthalene sulfonic acid series, sulfonated alkyl naphathalene series, organic sulfate series, organophosphate series, organic aliphatic acid series, sulfonated lignite and sulfonated gilsonite and derivative thereof, sulfonated petro-leum, sulfonated lignin.Described cats product comprises organic quaternary ammonium salt series, organic quaternary alkylphosphonium salt series and derivative thereof.Described nonionogenic tenside refers to organic acid acetic, polyoxyethylene sorbitan monooleate, sorbitan fatty acid ester.Described positively charged ion-nonionic amphoterics, negatively charged ion-nonionic amphoterics refers to the composite of described amphoterics and the amphoterics that has both the single type of described amphoteric character.The effect of tensio-active agent is different from the emulsifying effect of catalyzer.Described condensed-nuclei aromatics comprises benzene, naphthalene, phenanthrene, anthracene, quinoline, thiophene and comprises alkyl substituent of the above aromatic hydrocarbons and composition thereof, comprises also that in addition aromatic hydrocarbons extracts one or more in oil, catalytic slurry, carbolineum and the coal tar out.Described organic alcohol is the C of positive structure or isomery
1-C
22Monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol in one or more.Described organic carboxyl acid is the C of positive structure or isomery
1-C
22Monocarboxylic acid, di-carboxylic acid, tribasic carboxylic acid, quaternary carboxylic acid in one or more, also comprise in various naphthenic acid and the various aromatic acid one or more and the mixture of above-mentioned carboxylic acid; Described organic carboxylate is one or more in the monovalent salt, divalent salts, trivalent salt of above-mentioned organic carboxyl acid, promptly refers in basic metal, alkaline-earth metal, aluminium family metal and all subgroup elements one or more; In the acid amides that described organic carboxyl acid acid amides is above-mentioned organic carboxyl acid one or more; In the carboxylic acid halides that described organic carboxyl acid carboxylic acid halides is above-mentioned organic carboxyl acid one or more.Described Organophosphorous compounds are one or more in the phosphotriester of triphenylphosphate, triphenylphosphine, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, tricresyl phosphate naphthol ester and other types.The hydrogenation catalyst aid use temperature is less than 900 ℃.
Embodiment 1
Table 1 floating bed hydrogenation feedstock property
| Project | Raw material one | Raw material two |
| Density (20C)/gcm -3 | ????0.9442 | ????1.0085 |
| Viscosity (100C)/mm 2·s -1 | ????108.7 | ????744.2 |
| Elementary composition C/m% | ????86.6 | ????86.08 |
| ??????????H/m％ | ????12.5 | ????11.13 |
| ??????????N/m％ | ????0.41 | ????0.60 |
| ??????????S/m％ | ????0.13 | ????2.27 |
| ??????????V，PPm | ????1.8 | ????333.4 |
| ??????????Ni，PPm | ????81 | ????55.7 |
| ??????????Ca/μg/g | ????346 | ????47.3 |
| Carbon residue/m% | ????7.0 | ????18.66 |
| Saturated part of four components (m%) | ????50.4 | ????28.10 |
| Fragrance part (m%) | ????22.2 | ????37.63 |
| Colloid (m%) | ????27.2 | ????17.39 |
| Bituminous matter (m%) | ????0.2 | ????16.88 |
The present invention of table 2 intermittent reaction device is applicable to raw material one application example
| Blank | Example two | Example three | |
| Raw material type | Raw material one | Raw material one | Raw material one |
| Temperature of reaction, ℃ | ????440 | ????440 | ????440 |
| Reaction pressure, Mpa | ????7.0 | ????7.0 | ????7.0 |
| Primary Catalysts concentration, μ g/g | Constant | Constant | Constant |
| The auxiliary agent dosage, μ g/g | ????0 | ????500 | ????750 |
| Runtime, hour | ????1 | ????1 | ????1 |
| The raw material treatment capacity, g | ????200 | ????200 | ????200 |
| Yield (m%) | |||
| ＜180 ℃ of light oil+gases | ????23.3 | ????22.6 | ????21.5 |
| 180～360 ℃ of diesel oil | ????31.7 | ????30.0 | ????30.5 |
| 360～524 ℃ of wax oils | ????28.5 | ????30.6 | ????31.4 |
| ＞524 ℃ of residual oil | ????14.5 | ????15.0 | ????14.8 |
| The burnt content of liquid phases of reactants | ????2.0 | ????1.8 | ????1.8 |
| The reactor coking amount, gram | ????3.356 | ????0.610 | ????0.331 |
| Reactor coking amount reduced rate | ????-- | ????82％ | ????91％ |
Embodiment 2
The present invention of table 3 intermittent reaction device is applicable to raw material two application examples
| Blank | Example two | Example three | |
| Raw material type | Raw material two | Raw material two | Raw material two |
| Temperature of reaction, ℃ | ????435 | ????435 | ????435 |
| Reaction pressure, Mpa | ????7.0 | ????7.0 | ????7.0 |
| Primary Catalysts concentration, μ g/g | Constant | Constant | Constant |
| The auxiliary agent dosage, μ g/g | ????0 | ????500 | ????750 |
| Runtime, hour | ????1 | ????1 | ????1 |
| The raw material treatment capacity, g | ????200 | ????200 | ????200 |
| Yield (m%) | |||
| ＜180 ℃ of light oil+gases | ????15.7 | ????14.2 | ????13.0 |
| 180～360 ℃ of diesel oil | ????22.0 | ????22.0 | ????21.5 |
| 360～524 ℃ of wax oils | ????25.5 | ????26.6 | ????28.4 |
| ＞524 ℃ of residual oil | ????34.5 | ????34.5 | ????34.5 |
| The burnt content of liquid phases of reactants | ????3.3 | ????2.7 | ????2.6 |
| The reactor coking amount, gram | ????7.3730 | ????4.6237 | ????1.9957 |
| Reactor coking amount reduced rate | ????-- | ????38％ | ????73％ |
Embodiment 3
The present invention of table 4 continuous reaction apparatus is applicable to raw material one application example
| Blank | Example two | Example three | |
| Raw material type | Raw material one | Raw material one | Raw material one |
| Temperature of reaction, ℃ | ????450 | ????450 | ????450 |
| Reaction pressure, Mpa | ????11.0 | ????11.0 | ????11.0 |
| Air speed, H -1 | ????1.0 | ????1.0 | ????1.0 |
| Hydrogen-oil ratio, | ????800 | ????800 | ????800 |
| The auxiliary agent dosage, μ g/g | ????0 | ????500 | ????750 |
| Primary Catalysts | Constant | Constant | Constant |
| Runtime, day | ????10 | ????10 | ????10 |
| The raw material treatment capacity, Kg | ????200 | ????200 | ????200 |
| Yield (m%) | |||
| Gas | ????4.5 | ????3.4 | ????3.3 |
| ＜180 ℃ of light oil | ????15.6 | ????11.6 | ????11.6 |
| 180～360 ℃ of diesel oil | ????34.8 | ????33.8 | ????33.7 |
| 360～524 ℃ of wax oils | ????29.0 | ????34.5 | ????34.8 |
| ＞524 ℃ of residual oil | ????16.1 | ????16.7 | ????16.6 |
| The burnt content of liquid phases of reactants | ????1.50 | ????1.35 | ????1.30 |
| The reactor coking amount, gram | ????314.6 | ????40.6 | ????30.0 |
| Reactor coking amount reduced rate | ????-- | ????87.1％ | ????90.5％ |
From the foregoing description as can be seen, under the same conditions, use catalyst adjuvant provided by the present invention after, the coking amount on the reactor obviously reduces, and the add-on of auxiliary agent is big more, reactor coking amount reduced rate is high more.This is to develop owing to The present invention be directed to the hydrogenation of residual oil suspended bed process, under the multiple effect of catalyst adjuvant component, can form protective filmy layer in reactor surface, reduce the coking of reactor under the high temperature, the hydrogenation that helps simultaneously to improve catalyzer presses down burnt effect, and reduces at residual oil and reaction product and fail coking and the scale formation that reaches positions such as fractionation at furnace tubing, reaction tubes.
Claims (8)
1. hydrogenation of residual oil suspended bed auxiliary agent, it is characterized in that containing any one or any two kinds or arbitrarily two or more combination in the following material: natural organic high-molecular, synthetic organic polymer, natural surface active agent, synthetic surfactant, condensed-nuclei aromatics, organic alcohol, organic carboxyl acid, organic carboxylate, organic carboxyl acid acid amides, organic carboxyl acid carboxylic acid halides and Organophosphorous compounds, its addition are 10～8000 μ g/g of residual oil raw material.
2. according to the described hydrogenation of residual oil suspended bed auxiliary agent of claim 1, it is characterized in that said auxiliary agent is applied to the hydrogenation of residual oil suspended bed process, or be applied to the floating bed hydrogenation process that residual oil and coal or residual oil and plastic waste or residual oil and waste rubber or plastic waste and waste rubber hydrogenation refine process or coal liquefaction altogether.
3. according to the described hydrogenation of residual oil suspended bed auxiliary agent of claim 1, it is characterized in that said natural organic high-molecular or synthetic organic polymer are native starch, or Mierocrystalline cellulose, or polyoxyethylene glycol, or terephthalic acid ethylene glycol polycondensate, or terephthalic acid quadrol polycondensate, or other di-carboxylic acid ethylene glycol polycondensate, or other di-carboxylic acid diamine polycondensate, comprise the above modifier natural or synthetic polymer simultaneously, polyacrylamide, polyacrylonitrile, partially hydrolyzed polyacrylamide, resol and their derivative also comprise polyethylene, or polypropylene, or polystyrene and their modifier and derivative; The molecular weight ranges of described natural organic high-molecular or synthetic organic polymer is 100～20000000.
4. according to the described hydrogenation of residual oil suspended bed auxiliary agent of claim 1, it is characterized in that said tensio-active agent comprises aniorfic surfactant, cationic surfactant, nonionogenic tenside, positively charged ion one nonionic amphoterics, negatively charged ion-nonionic amphoterics; Said anion surfactant refers to alkyl benzene sulphonate (ABS) series, alkylbenzene sulfonate series, alkyl naphthalene sulfonic acid series, sulfonated alkyl naphathalene series, organic sulfate series, organophosphate series, organic aliphatic acid series, sulfonated lignite and sulfonated gilsonite and derivative thereof, sulfonated petro-leum, sulfonated lignin; Said cats product comprises organic quaternary ammonium salt series, organic quaternary alkylphosphonium salt series and derivative thereof; Said nonionogenic tenside refers to organic acid acetic, polyoxyethylene sorbitan monooleate, sorbitan fatty acid ester; Said positively charged ion-nonionic amphoterics, negatively charged ion-nonionic amphoterics refer to the composite of described amphoterics and the amphoterics that has both the single type of described amphoteric character.
5. according to the described hydrogenation of residual oil suspended bed auxiliary agent of claim 1, it is characterized in that said condensed-nuclei aromatics comprises benzene, naphthalene, phenanthrene, anthracene, quinoline, thiophene and comprises alkyl substituent of the above aromatic hydrocarbons and composition thereof, also comprise in aromatic hydrocarbons extraction oil, catalytic slurry, carbolineum and the coal tar one or more in addition.
6. according to the described hydrogenation of residual oil suspended bed auxiliary agent of claim 1, it is characterized in that said organic alcohol is the C of positive structure
1-C
22Monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol in one or more, or be the C of isomery
1-C
22Monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol in one or more.
7. according to the described hydrogenation of residual oil suspended bed auxiliary agent of claim 1, it is characterized in that said organic carboxyl acid is the C of positive structure
1-C
22Monocarboxylic acid, di-carboxylic acid, tribasic carboxylic acid, quaternary carboxylic acid in one or more, or be the C of isomery
1-C
22Monocarboxylic acid, di-carboxylic acid, tribasic carboxylic acid, quaternary carboxylic acid in one or more, also comprise in various naphthenic acid and the various aromatic acid one or more, and the mixture of above-mentioned carboxylic acid, also comprise in various naphthenic acid and the various aromatic acid one or more and the mixture of above-mentioned carboxylic acid; Said organic carboxylate is one or more in the monovalent salt, divalent salts, trivalent salt of above-mentioned organic carboxyl acid, promptly refers to basic metal, alkaline-earth metal, one or more in aluminium family metal and all subgroup elements; In the acid amides that said organic carboxyl acid acid amides is above-mentioned organic carboxyl acid one or more; In the carboxylic acid halides that said organic carboxyl acid carboxylic acid halides is above-mentioned organic carboxyl acid one or more.
8. according to the described hydrogenation of residual oil suspended bed auxiliary agent of claim 1, it is characterized in that described Organophosphorous compounds are one or more in the phosphotriester of triphenylphosphate, triphenyl phosphorus, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, tricresyl phosphate naphthol ester and other types.
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| CN106914275A (en) * | 2015-12-28 | 2017-07-04 | 中国石油天然气股份有限公司 | The preparation method of residual oil slurry bed hydrogenation catalyst |
| CN106914275B (en) * | 2015-12-28 | 2019-06-11 | 中国石油天然气股份有限公司 | The preparation method of residual oil slurry bed hydrogenation catalyst |
| CN109219649A (en) * | 2016-03-18 | 2019-01-15 | 韩国化学研究院 | By means of the heavy oil conversion method of asphalitine enhancement of dispersion |
| CN109219649B (en) * | 2016-03-18 | 2021-01-15 | 韩国化学研究院 | Heavy oil conversion process with high asphaltene dispersancy |
| CN114163826A (en) * | 2020-09-11 | 2022-03-11 | 中国石油化工股份有限公司 | Color-paved cementing material and preparation method and application thereof |
| CN115261061A (en) * | 2022-08-08 | 2022-11-01 | 徐文忠 | Non-fixed bed hydrogenation synergistic deslagging process |
| CN115261061B (en) * | 2022-08-08 | 2023-09-15 | 徐文忠 | Non-fixed bed hydrogenation synergistic deslagging process |
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