CN102343287B - Oily dispersion medium for solid powder catalyst, preparation method and application thereof - Google Patents
Oily dispersion medium for solid powder catalyst, preparation method and application thereof Download PDFInfo
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- CN102343287B CN102343287B CN201010239889.0A CN201010239889A CN102343287B CN 102343287 B CN102343287 B CN 102343287B CN 201010239889 A CN201010239889 A CN 201010239889A CN 102343287 B CN102343287 B CN 102343287B
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Abstract
The invention relates to an oily dispersion medium for a solid powder catalyst, a preparation method and application thereof. The oily dispersion medium comprises, based on the oily dispersion medium: 85-99 wt% of base oil, 0.05-10 wt% of an ionic surfactant, and 0.05-10 wt% of a solid thickening rheological agent. Specifically, the base oil is distillate oil with a boiling point ranging from 220DEG C to 550DEG C. The oily dispersion medium provided in the invention can enable high concentration and long-term stable dispersion of Mo, Fe, Ni, Co, W and other active metal sulfides and/or oxides, so that catalyst oil slurry consumption in present technologies can be reduced substantially, and influence of oil slurry on heavy oil properties can be lessened. Meanwhile, homodisperse of active metals in oil can be realized.
Description
Technical field
The present invention relates to a kind of oiliness decentralized medium, more particularly, is a kind of oiliness decentralized medium of the pressed powder type catalyst for heavy-oil hydrogenation, and the preparation method and application of this oiliness decentralized medium.
Background technology
Heavy oil slurry state bed hydroprocessing technique is a kind of important heavy oil modification approach, and reason is that its adaptability to inferior heavy oil is high, and process flexibility is high, can realize Efficient Conversion and pretreated requirement by adjusting its conversion ratio.
Heavy petroleum asphalt matter and carbon residue content are high, generally contain the impurity such as metal, S, N of high-load, and apparent viscosity is large, and in heat treatment or hydrotreatment process, heavy oil component is easily assembled sedimentation green coke.Therefore improving catalyst dispersiveness and hydrocracking performance in feedstock oil is to improve two key factors of heavy oil modification effect.At present conventional heavy oil slurry state bed hydroprocessing catalysts for treating comprises pressed powder type heterogeneous catalysis and oil-soluble, water-soluble homogeneous catalyst, the former in the dispersibility in heavy oil a little less than homogeneous catalyst.
But, use the weak point of homogeneous catalyst to be, the ratio of its active metal component, as low in the ratio of metal molybdenum, be difficult to exceed 20% of gross mass, be only generally 6.5～9.0%.As the oil-soluble heavy-oil hydrogenation Cracking catalyst of CN1362492A a kind of phenylhydroxylamine that contains Mo, W of proposition and derivative complex compound thereof.According to this patent working example, in the catalyst that conventional method obtains, molybdenum content is 7.0%.And for example CN 1335367A has disclosed a kind of oil-soluble catalyst that contains heterocycle sulfo group compound, and for containing the organic solid product of one or more metals such as Cr, Ni, Fe, Co, Mo, W, tenor is lower than 9%.CN101165140A and CN101165141A have proposed isooctyl acid molybdenum and molybdenum naphthenate catalyst, are the oily of thickness, and tenor is higher than 6%, for coal oil refining process.In use, for guaranteeing the concentration of active metal in feedstock oil, addition is large, has improved application cost on the one hand for this type of catalyst, and the oil-catalyst slurry adding in a large number has on the other hand affected feedstock oil nature.
While using water-soluble catalyst, generally the presoma salt that contains active metal to be dissolved in the aqueous solution, for improving the dispersiveness of the aqueous solution in feedstock oil, except improving physical agitation intensity, as narrated a kind of method of water-soluble catalyst being disperseed online by multistage shear pump or static mixer in CN 1295112A; Maybe need to add dispersant and surface active agent composition, as University of Petroleum proposes two kinds of catalyst lyosol systems in patent CN 101024186A and CN 101011663A, difference is that the former is Water-In-Oil system, the latter is oil-in-water system, the metal sulfide complexings such as Mo, Ni, Fe, Co are dispersed in sol system, and tenor is generally lower than 15% of gross mass, and use amount is larger, in use procedure, also to remove moisture, complicated operation.
Summary of the invention
The object of this invention is to provide a kind of oiliness decentralized medium of pressed powder type catalyst, preparation method and application, to be solved is to adopt in the slurry state bed or suspension bed hydrogenation process process of solid powder th-1 catalyst, the stable dispersion performance poor technical problem of pressed powder type catalyst in heavy oil feedstock oil.
The oiliness decentralized medium of pressed powder type catalyst provided by the invention, contain following composition: take oiliness decentralized medium as benchmark, the base oil of 85～99 % by weight, 0.05～10 % by weight ionic surfactant, 0.05～10 % by weight solid thickener rheology agent, described base oil is boiling spread at the distillate of 220 ℃～550 ℃.
The particle diameter of pressed powder type catalyst of the present invention is less than 50 μ m, contains the active metal that is selected from Mo, Fe, Ni, Co, W one or more.This solid powder th-1 catalyst is for the slurry state bed of heavy oil or the hydrotreatment process of suspension bed.
Described base oil is selected from one or more in diesel oil, kerosene, wax oil.
Described ionic surfactant is selected from one or more in enuatrol, neopelex, petroleum sodium sulfonate and fatty acid quaternary ammonium salt.Preferably, the consumption of described ionic surfactant is 0.1～5.0 % by weight.
Described solid thickener rheology agent is selected from one or more in amorphous silica, magnesium aluminate, magnesium silicate, organobentonite, and the particle diameter of solid thickener rheology agent is less than 100 μ m, is preferably less than 20 μ m, is more preferably less than 1 μ m.Preferably, the consumption of described solid thickener rheology agent is 0.1～5.0 % by weight.
A preparation method for above-mentioned any oiliness decentralized medium, comprising:
(1) base oil mixed with solid thickener rheology agent and homogenize with cutter;
(2) be heated to 40～120 ℃, process 0.5～3 hour;
(3) be down to room temperature, add ionic surfactant, be at room temperature stirred to system homogeneous phase.
In another embodiment, also contain nonionic surface active agent in oiliness decentralized medium, take oiliness decentralized medium as benchmark, consumption is 0.05～10 % by weight.Described nonionic surface active agent is polyethylene glycol (PEG) and/or polyvinyl alcohol, and wherein the number-average molecular weight of polyethylene glycol is 400-6000, the polyvinyl alcohol with low degree of polymerization of polyvinyl alcohol.Preferably, described nonionic surface active agent, take oiliness decentralized medium as benchmark, consumption is 0.1～5 % by weight.
A preparation method for the above-mentioned oiliness decentralized medium that any contains nonionic surface active agent, comprising:
(1) base oil mixed with solid thickener rheology agent and homogenize with cutter;
(2) be heated to 40～120 ℃, process 0.5～3 hour;
(3) be down to room temperature, add ionic surfactant and non-ionic surface active agent, be at room temperature stirred to system homogeneous phase.
In another embodiment, in oiliness decentralized medium, also contain any and can improve auxiliary agent or the additive of pressed powder type catalyst in oiliness decentralized medium stable dispersion performance.
An application for above-mentioned any oiliness decentralized medium, is dispersed in pressed powder type catalyst in described oiliness decentralized medium, and for starching the heavy-oil hydrogenation process of state bed or suspension bed.
The main cause that oiliness decentralized medium of the present invention has dispersibility is: the polar end of the surfactant containing in this oiliness decentralized medium can be adsorbed on pressed powder surface and form micelle, and the non-polar end of surfactant has high compatibility in oiliness decentralized medium, form micelle structure, make the pressed powder can be dispersed in oiliness decentralized medium.
Oiliness decentralized medium provided by the present invention, the solid powder th-1 catalyst that can make particle diameter be less than 50 μ m is pre-dispersed in this oiliness decentralized medium with high concentration, and sedimentation can not occur for a long time.Then mix with heavy oil feedstock oil in use, can obtain the finely disseminated feedstock oil of catalyst, and have good heavy-oil hydrogenation catalytic activity.
Oiliness decentralized medium provided by the present invention, can make the long-time stable dispersion of high concentration of Mo, Fe, Ni, Co, W isoreactivity metal sulfide and/or oxide.Thereby significantly reduce the consumption of oil-catalyst slurry in prior art, reduce the impact of slurry oil counterweight oil nature, realize dispersed in oil of active metal simultaneously.
The specific embodiment
Below by embodiment, oiliness decentralized medium provided by the invention is illustrated further, but not thereby limiting the invention.
Embodiment 1
Weigh diesel oil 38.5g, (particle diameter is less than 20 μ m), homogenizes with cutter to add magnesium silicate 1.0g.Be heated to stir 2 hours at 65 ℃, the homogeneous miscella obtaining is chilled to room temperature, then adds 0.5g enuatrol, under normal temperature, homogenizes, and obtains oiliness decentralized medium A.Take the gross weight of the oiliness decentralized medium that obtains as benchmark, in oiliness decentralized medium A, contain 96.2% base oil, contain 2.5% solid thickener rheology agent and 1.3% ionic surfactant.
Embodiment 2
Weigh diesel oil 38g, (particle diameter is less than 30 μ m), on cutter, homogenizes to add organobentonite 1.0g.Then in 80 ℃ of oil baths, add thermal agitation 2 hours.The homogeneous miscella obtaining is chilled to room temperature, adds 0.5g PEG 600, adds 0.2g neopelex, under normal temperature, homogenizes, and obtains oiliness decentralized medium B.
Take oiliness decentralized medium weight as benchmark, it specifically consists of: contain 95.7% base oil, 0.5% ionic surfactant, 2.5% solid thickener rheology agent and 1.3% nonionic surfactant.
Embodiment 3
Weigh kerosene 42g, (particle diameter is less than 1 μ m), homogenizes with cutter to add aerosil 0.8g, be heated to 80 ℃ and stir 2 hours, be cooled to normal temperature, add 0.5g PEG2000, then add enuatrol 0.3g, under normal temperature, homogenize, obtain oiliness decentralized medium C.
Take oiliness decentralized medium weight as benchmark, it specifically consists of: contain 96.3% base oil, 1.8% solid thickener rheology agent, 0.7% ionic surfactant and 1.2% nonionic surface active agent.
Embodiment 4
Take the pure WS of the commercially available analysis of 4.0g
3, its average grain diameter is less than 15 μ m, and itself and 9.0g oiliness decentralized medium A are placed in to same test tube, and glass bar stirs and vibrates, and after powder infiltrates evenly, leaves standstill 6 hours, occurs without obvious sedimentation.
Embodiment 5
Get commercially available MoS
2, average grain diameter is less than 30 μ m, weighs 3.0g and is placed in test tube.Weigh 5.0g oiliness decentralized medium B in same test tube, glass bar stirs and vibrates, and after powder infiltrates evenly, leaves standstill 24 hours, and nothing obviously sedimentation occurs.
Embodiment 6
Get and analyze pure MoO
3, in agate mortar, grind and sieve out and be less than 200 object pressed powders (average grain diameter approximately 80 μ m).Weigh 5.0g and be placed in test tube.Weigh 10.0g oiliness decentralized medium C in same test tube, glass bar stirs and vibrates, and after powder infiltrates evenly, leaves standstill 12 hours, and nothing obviously sedimentation occurs.
Comparative example 1
(20 ℃ of viscosity are 20.0m to weigh white oil 5.0g
2/ S) in test tube, weigh the commercially available MoS of 0.6g
2(average grain diameter is less than 30 μ m) in same test tube, and glass bar stirs and vibrates, and after powder infiltrates evenly, leaves standstill after 5 hours obviously layering.
Comparative example 2
(20 ℃ of viscosity are 42.0m to weigh lube base oil 10.0g
2/ S) in test tube, weigh 1.0gMoO
3(average grain diameter approximately 80 μ are m) in same test tube, and glass bar stirs and vibrates, and after powder infiltrates evenly, leave standstill after 6 hours obviously layering.
Claims (10)
1. the oiliness decentralized medium of a pressed powder type catalyst, composed of the following components: take oiliness decentralized medium as benchmark, the base oil of 85～99 % by weight, 0.05～10 % by weight ionic surfactant, 0.05～10 % by weight solid thickener rheology agent, 0.05～10 % by weight nonionic surface active agent, each component weight percentage sum is 100%, described base oil is boiling spread at the distillate of 220 ℃-550 ℃, described nonionic surface active agent is polyethylene glycol and/or polyvinyl alcohol, wherein the number-average molecular weight of polyethylene glycol is 400-6000, polyvinyl alcohol is polyvinyl alcohol with low degree of polymerization, the particle diameter of described pressed powder type catalyst is less than 50 μ m, contain and be selected from Mo, Fe, Ni, Co, the active metal of one or more in W.
2. according to oiliness decentralized medium claimed in claim 1, it is characterized in that, described base oil is selected from one or more in diesel oil, kerosene, wax oil.
3. according to oiliness decentralized medium claimed in claim 1, it is characterized in that, described ionic surfactant is selected from one or more in enuatrol, neopelex, petroleum sodium sulfonate and fatty acid quaternary ammonium salt.
4. according to oiliness decentralized medium claimed in claim 1, it is characterized in that, the consumption of described ionic surfactant is 0.1～5.0 % by weight.
5. according to oiliness decentralized medium claimed in claim 1, it is characterized in that, described solid thickener rheology agent is selected from one or more in amorphous silica, magnesium aluminate, magnesium silicate, organobentonite, and the particle diameter of solid thickener rheology agent is less than 100 μ m.
6. according to oiliness decentralized medium claimed in claim 4, it is characterized in that, the particle diameter of described solid thickener rheology agent is less than 20 μ m.
7. according to oiliness decentralized medium claimed in claim 1, it is characterized in that, the consumption of described solid thickener rheology agent is 0.1～5.0 % by weight.
8. according to oiliness decentralized medium claimed in claim 1, it is characterized in that, described nonionic surface active agent, take oiliness decentralized medium as benchmark, consumption is 0.1～5 % by weight.
9. a preparation method for any oiliness decentralized medium of claim 1-8, comprising:
(1) base oil mixed with solid thickener rheology agent and homogenize with cutter;
(2) be heated to 40～120 ℃, process 0.5～3 hour;
(3) be down to room temperature, add ionic surfactant and non-ionic surface active agent, be at room temperature stirred to system homogeneous phase.
10. an application for any oiliness decentralized medium of claim 1-8, is dispersed in pressed powder type catalyst in described oiliness decentralized medium, and for starching the heavy-oil hydrogenation process of state bed or suspension bed.
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| CN103285929B (en) * | 2012-02-22 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst of aluminiferous ore and Synthesis and applications thereof |
| CN103285928B (en) * | 2012-02-22 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst containing ferric oxide ore and Synthesis and applications thereof |
| CN103285930B (en) * | 2012-02-22 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst containing yellow iron and Synthesis and applications thereof |
| CN111644208B (en) * | 2020-06-17 | 2023-04-07 | 中国石油大学(华东) | Preparation method and application of oil-soluble suspension bed hydrogenation catalyst |
| CN112871219B (en) * | 2021-01-14 | 2022-09-06 | 上海阳申石化设备安装有限公司 | Flame-retardant composition for hydrogenation catalysis and use method thereof |
| CN114181733B (en) * | 2021-11-25 | 2023-06-30 | 中国石油大学(华东) | Method for regulating particle size of vulcanized product of oil-soluble catalyst |
| CN114618584B (en) * | 2022-04-01 | 2024-02-20 | 泰戈特（北京）工程技术有限公司 | Oil-soluble iron-based catalyst and preparation method and application thereof |
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| CN1433692A (en) * | 2003-03-05 | 2003-08-06 | 湖北省林业科学研究院 | Bacillus thuringiensis oil suspension concentrate pesticide |
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