CN101024186A - Reversed phase micelle nano catalyst for dreg-oil suspension bed hydrogenation cracking and preparing method - Google Patents
Reversed phase micelle nano catalyst for dreg-oil suspension bed hydrogenation cracking and preparing method Download PDFInfo
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Abstract
The invention discloses a catalyst for low quality heavy oil or residue suspended bed hydrocracking and preparation method belongs to oil process technology area. The catalyst is a sulfurization form transition metal nm particle that existing in the reversed phase micelle colloidal solution, the disperse medium of reversed phase micelle colloidal solution is organic phase, the disperse phase is a water phase parceled by surface activity, sulfurization form transition metal nm particle steady consist in the water phase. The transition metal active ingredient in disperse phase elect as Cu,Mn,Fe,Co,Ni,Cr,Mo,W,Zn,Sn,Pb elementary sulfurization form particle and so on, the grain size between 1nm-1000um. This catalyst can uniformly dispersed in the low quality heavy oil,residue, and under the certain reaction temperature and hydrogen aura, the low quality heavy oil or residue containing catalyst through suspended bed hydrocracking translated into light oil. On the premise of reducing catalyst enter quantity, the invention effectively controlled the coking products in heavy oil or residue suspended bed hydrocracking process, improved the yield of light oil.
Description
Technical field:
The present invention relates to the Catalysts and its preparation method of a kind of inferior heavy oil, dreg-oil suspension bed hydrogenation cracking, belong to PETROLEUM PROCESSING and petrochemical technology field.
Background technology:
At present, it is heavy that the crude oil of domestic exploitation becomes day by day, and the heavy crude of import and residual oil amount also constantly increase, and market is increasing to the demand of light-end products, therefore people more and more pay attention to heavy oil lighting technology, and the heavy oil floating bed hydrocracking technology is exactly one of technology that receives much concern.Because the heavy oil floating bed hydrocracking technology has also generated a large amount of coke at inside reactor when guaranteeing higher light-end products yield, influenced the long-term operation of reactor.So the green coke problem in the heavy oil floating bed hydrogenation technology becomes the major issue that presses for solution, the new catalyst of researching and developing efficiently, be suitable for the heavy oil floating bed hydrogenation process characteristic more and more causes the great attention on oil refining circle.
At present, the water-soluble catalyst typical technology that is used for heavy oil floating bed hydrogenation has Exxon company to make catalyst with phosphomolybdic acid and Chevron company makes catalyst with ammonium molybdate.In the research of oil-soluble catalyst, there is United States Patent (USP) 4579838 to announce, obtains oil-soluble di-t-butyl chromate, it is mixed with part heavy oil, in the presence of hydrogen sulfide gas, add hot mixt then, obtain catalyst with chromium oxide and alcohol reaction.Heating condition is 370～427 ℃, 0.7～14MPa, and chromium content is 0.1～2.0m% in the gained slurry catalyst.This catalyst is used for the heavily floating bed hydrogenation of Arabic decompression residuum, reaction pressure 14.4MPa, 443 ℃ of reactions down when the addition of catalyst is 350 μ g/g, are 84.6m% greater than 524 ℃ of cut conversion ratios, coking yield is 1.43m%.Adopt Fe (CO) in the United States Patent (USP) 5578197
5With the 2 ethyl hexanoic acid molybdenum be catalyst, is raw material to contain 60m% greater than 504 ℃ residual oil, the catalyst addition is 5000 μ g/g, and add diluent in 2: 1 ratio, on autoclave, test 430 ℃ of reaction temperatures, reaction pressure 10.0MPa, 105 minutes reaction time was 27.0m% greater than 504 ℃ liquid yields, and coke is 3.8m%.When United States Patent (USP) 4125455 adopted molybdenum caprylates to be catalyst, as metal addition 590 μ g/g, the reaction time was when being 8 hours, was 80.0m% greater than the conversion ratio of 454 ℃ of cuts.One or more metals in the Chinese patent 00110711.9 application element periodic table in group vib, VIIB family and the group VIII with contain the formed complex compound of heteroatomic heterocycle sulfo group compound as catalyst, wherein metallic element includes iron, cobalt, nickel, chromium, molybdenum, tungsten; Chinese patent 01109276.9 is used the aqueous solution of iron, nickel, cobalt, molybdenum as catalyst.Still there are some shortcomings in above-mentioned catalyst, as catalyst cost an arm and a leg, the active component addition is big, dispersion effect in feedstock oil is poor, degree is high and press down burnt weak effect or the like fully in sulfuration.
Summary of the invention:
The objective of the invention is in order to develop a kind of reversed phase micelle nano catalyst that is used for dreg-oil suspension bed hydrogenation cracking and preparation method thereof.This catalyst is used for the heavy oil floating bed hydrocracking technical process, in raw material, highly evenly disperse under the situation that can make catalytic active component guarantee that higher sulfuration spends fully, can suppress the coking of reactor and boiler tube in the heavy oil floating bed hydrogenation process effectively, solve the long-term operation problem of heavy oil floating bed hydrocracking technology.
The object of the present invention is achieved like this, the catalyst that is provided is a kind of reversed phase micelle solution, its composition comprises: as the organic facies of decentralized medium, decentralized photo is the water by the surfactant parcel, active component is a kind of sulphided state transition metal sodium rice particle, and stable existence is in the aqueous phase of reversed phase micelle colloidal solution.Specifically consisting of of this reversed phase micelle nano catalyst system: the content of organic facies is 50～90m%, and water content is 0.1～30m%, and the content of transition metal active component is 8～45% in the aqueous solution, and the content of surfactant is 0.01～10.0m%.
Transition metal active component in the decentralized photo is the sulfide of one or more transition metals among group VIII, VIB and the VIIB in the periodic table of elements, the sulphided state particle of elements such as Cu, Mn, Fe, Co, Ni, Cr, Mo, W, Zn, Sn or Pb preferably, particle diameter is between 1nm～1000 μ m.It is in the reversed phase micelle colloidal dispersion of decentralized medium that active metal component is evenly distributed on the organic facies.The organic facies decentralized photo of this reversed phase micelle colloidal dispersion is for comprising C
5Two components or the ternary mixture of above various linear paraffins, aromatic hydrocarbon, cycloalkane and linear paraffin, aromatic hydrocarbon or cycloalkane perhaps are a kind of or mixture each other in naphtha, benzinum, gasoline, diesel oil, the vacuum distillate; Applied surface active agent composition is one or more in alkyl benzene sulphonate series, alkylbenzenesulfonate series, alkyl naphthalene sulfonic acid series, alkylnaphthalene sulfonate series, petroleum sulfonate, ligninsulfonate, organic aliphatic acid series, organic phosphate series, organic quaternary ammonium salt series, the organic quaternary alkylphosphonium salt series in the catalyst preparation process.
Preparation of catalysts method: with the aqueous solution of the soluble metallic salt of one or more transition metals among group VIII, VIB and the VIIB in the periodic table of elements, among the preferred Cu of transition metal, Mn, Fe, Co, Ni, Cr, Mo, W, Zn, Sn, the Pb one or more, under 10～80 ℃ of conditions, according to reversed phase micelle colloidal dispersion water content is that the addition of 0.1～30.0m% joins in the mixed solution of organic facies and surfactant, and wherein organic facies is C
5Above various linear paraffins, aromatic hydrocarbon, cycloalkane and linear paraffin, two components or the ternary mixture of aromatic hydrocarbon or cycloalkane, it perhaps is naphtha, benzinum, gasoline, diesel oil, a kind of or mixture each other in the vacuum distillate, surfactant is an alkyl benzene sulphonate series, alkylbenzenesulfonate series, alkyl naphthalene sulfonic acid series, alkylnaphthalene sulfonate series, petroleum sulfonate, ligninsulfonate, organic aliphatic acid series, organic phosphate series, organic quaternary ammonium salt series, in organic quaternary alkylphosphonium salt series one or more, the content of organic facies is 50～90m%, and the content of surfactant is 0.01～10.0m%.Stirred 0.5～1.5 hour, and slowly added the vulcanizing agent aqueous solution then, reacted 0.5～1.5 hour, be cooled to room temperature and promptly obtain required catalyst system.
In above-mentioned preparation process, the adding order of the catalyst and the vulcanizing agent aqueous solution can exchange, and also can prepare the reversed phase micelle system of the catalyst and the vulcanizing agent aqueous solution respectively, and hybrid reaction makes reversed phase micelle nano catalyst then.
The advantage of this catalyst is: (1) sulphided state active component height evenly disperses, and does not have any deposition or coalescence phenomenon; (2) degree is high fully for the sulfuration of activity of such catalysts metal component, highly evenly disperses in raw material residual oil easily, and it is active high to suppress green coke; (3) the catalyst addition is few, has saved production cost greatly.
The specific embodiment:
Below in conjunction with embodiment, specify the preparation and the application of reversed phase micelle nano catalyst provided by the present invention.
Using the operating condition that this catalyst carries out the dreg-oil suspension bed hydrogenation cracking reaction under the usual conditions is: reaction pressure is 3～20MPa, and reaction temperature is 400～480 ℃, liquid hourly space velocity (LHSV) 0.3～2.5h
-1, hydrogen to oil volume ratio is 300～1200 under the normal pressure.
Embodiment 1, gets organic facies toluene 45g, and surfactant organic quaternary ammonium salt 1g, cosurfactant methyl alcohol 0.5g, three constant temperature under 40 ℃ of conditions stirred 10 minutes, when constant speed stirs, slowly dripped the CuCl of 1.0mol/l then
2The about 10ml of salting liquid stablized under the sealed thermostat condition 0.5 hour, was cooled to room temperature and left standstill, and promptly got the catalyst metal salts micro emulsion.Get the vulcanized sodium 10ml of 1.2mol/l, under 40 ℃ of constant temperature stirring conditions, slowly be added drop-wise in the above-mentioned gained micro emulsion, reaction is 0.5 hour under controlled condition, is cooled to room temperature and leaves standstill, and promptly gets the reversed phase micelle nano system of sulphided state catalyst.
Embodiment 2, get organic facies diesel oil 45g, and the organic quaternary alkylphosphonium salt 3g of surfactant, surfactant T-80 2g, cosurfactant methyl alcohol 5g, three constant temperature under 40 ℃ of conditions stirred 10 minutes, when constant speed stirs, slowly dripped the CuCl of 2.0mol/l then
2Salting liquid 8ml stablized under the sealed thermostat condition 0.5 hour, was cooled to room temperature and left standstill, and promptly got the catalyst metal salts micro emulsion.Get the sulfuration ammonia 2ml of 2.5mol/l, under 40 ℃ of constant temperature stirring conditions, slowly be added drop-wise in the above-mentioned gained micro emulsion, reaction is 0.5 hour under controlled condition, is cooled to room temperature and leaves standstill, and promptly gets the reversed phase micelle nano system of sulphided state catalyst.
Embodiment 3, get organic facies dimethylbenzene 45g, surfactant petroleum sulfonate 3g, surfactant T-80 2g, cosurfactant methyl alcohol 4g, three constant temperature under 40 ℃ of conditions stirred 10 minutes, then when constant speed stirs, slowly drip the potassium sulfide 1ml of 2.5mol/l, stablized under the sealed thermostat condition 0.5 hour, promptly get the catalyst metal salts micro emulsion.Get the Co (NO3) of 2.0mol/l
2Salting liquid 0.5ml under 40 ℃ of constant temperature stirring conditions, slowly is added drop-wise in the above-mentioned gained micro emulsion, and reaction is 0.5 hour under controlled condition, is cooled to room temperature and leaves standstill, and promptly gets the reversed phase micelle nano system of sulphided state catalyst.
Embodiment 4, get 60 ℃～90 ℃ benzinum 50g of organic facies, surfactant benzene sulfonate 2g, surfactant T-80 0.5g, cosurfactant methyl alcohol 2g, three constant temperature under 40 ℃ of conditions stirred 10 minutes, when constant speed stirs, drip the NiCl of 2.0mol/l then
2Salting liquid 0.5ml stablized under the sealed thermostat condition 0.5 hour, promptly got the catalyst metal salts micro emulsion.Get organic facies, surfactant, the same mixing of cosurfactant, constant temperature stirred 10 minutes under 40 ℃ of conditions, when constant speed stirs, slowly dripped the sulfuration ammonia 1ml of 2.5mol/l then, stablized under the sealed thermostat condition 0.5 hour, and promptly got the catalyst metal salts micro emulsion.Under 40 ℃ of constant temperature stirring conditions, above-mentioned gained two micro emulsions are mixed mutually, reaction is 0.5 hour under controlled condition, is cooled to room temperature and leaves standstill, and promptly gets the reversed phase micelle nano system of sulphided state catalyst.
Embodiment 5 batch reactor catalyst application examples.
Table 1 hydrogenation of residual oil suspended bed feedstock property
| Project | Raw material |
| Density (20 ℃)/gcm -3 | 0.9442 |
| Viscosity (100 ℃)/mm 2·s -1 | 108. |
| Freezing point (℃) | 2.0 |
| Carbon residue (w%) | 7.0 |
| Ash content (w%) | 0.085 |
| The saturated branch of four components (m%) | 50.4 |
| Fragrance divides (m%) | 22.2 |
| Colloid (m%) | 27.2 |
| Asphalitine (m%) | 0.2 |
| Element is formed C/m% | 86.6 |
| H/m％ | 12.5 |
| N/m％ | 0.41 |
| S/m％ | 0.13 |
| V/m％ | 0.35 |
| Ni/m％ | 11.8 |
| Fe/m％ | 10.2 |
| Ca/m％ | 346 |
Application of Catalyst result provided by the present invention under the table 2 intermittent reaction condition
| Project | Blank | Example 1 | Example 2 | Example 4 |
| Reaction pressure, MPa | 7.0 | 7.0 | 7.0 | 7.0 |
| Reaction temperature, ℃ | 430 | 430 | 430 | 430 |
| The catalyst activity concentration of component | 0 | Constant (catalyst that adds embodiment 1) | Constant (catalyst that adds embodiment 2) | Constant (catalyst that adds embodiment 3) |
| Reaction time, hour | 1.0 | 1.0 | 1.0 | 1.0 |
| The raw material treating capacity, g | 250 | 250 | 250 | 250 |
| Yield (m%) | ||||
| Gas+＜180 ℃ gasoline | 22.4 | 21.9 | 21.5 | 22.3 |
| 180 ℃～360 ℃ diesel oil | 30.8 | 30.2 | 29.5 | 29.6 |
| 360 ℃～524 ℃ wax oils | 29.6 | 30.5 | 31.5 | 305 |
| ＞524 ℃ of residual oil | 15.4 | 16.0 | 15.6 | 15.9 |
| The total burnt amount of product, g | 4.86 | 1.51 | 1.26 | 1.82 |
| Catalyst always presses down burnt rate | -- | 68.93％ | 74.07％ | 62.55％ |
Embodiment 6 flow reactor catalyst application examples
Table 3 is at continuous reaction apparatus catalyst application result provided by the present invention
(feedstock property sees Table 1)
| Project | Blank | Example 1 | Example 2 | Example 4 |
| Reaction pressure, MPa | 11.0 | 11.0 | 11.0 | 11.0 |
| Reaction temperature, ℃ | 450 | 450 | 450 | 450 |
| Air speed, h -1 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen-oil ratio | 800 | 800 | 800 | 800 |
| The duration of runs, hour | 240 | 240 | 240 | 240 |
| The raw material treating capacity, Kg | 200 | 200 | 200 | 200 |
| The catalyst activity concentration of component | Aqueous catalyst (constant) | Constant (catalyst that adds embodiment 1) | Constant (catalyst that adds embodiment 2) | Constant (catalyst that adds embodiment 3) |
| Yield (m%) | ||||
| Gas | 4.5 | 3.3 | 3.0 | 3.6 |
| ＜180 ℃ of gasoline | 15.6 | 11.1 | 10.7 | 11.5 |
| 180 ℃～360 ℃ diesel oil | 34.8 | 33.2 | 32.9 | 33.7 |
| 360 ℃～524 ℃ wax oils | 29.0 | 34.8 | 35.5 | 33.9 |
| ＞524 ℃ of residual oil | 16.1 | 17.6 | 17.9 | 17.3 |
| The burnt content of liquid phases of reactants, g | 1.51 | 1.26 | 1.2 | 1.35 |
| The reactor coking amount, g | 114.6 | 47.3 | 37.4 | 54.6 |
| Reactor coking reduced rate | -- | 58.73％ | 67.36％ | 52.36％ |
From the foregoing description as can be seen, the reversed phase micelle nano system that makes under the different condition can be used as the dreg-oil suspension bed hydrogenation cracking catalyst, be applied in the floating bed hydrogenation reaction process of some poor residuums or viscous crude, in reaction pressure is 3～20MPa, reaction temperature is 400～480 ℃, liquid hourly space velocity (LHSV) 0.3～2.5h
-1Hydrogen to oil volume ratio is 300～1200 o'clock under the normal pressure, the addition of catalyst (in metal active constituent) is 50～800 μ g/g, and the activity of good restraining reaction condensation green coke and the coking of inhibitory reaction device is arranged in the reaction of heavy oil (or residual oil) floating bed hydrocracking.
Claims (5)
1. reversed phase micelle nano catalyst that is used for dreg-oil suspension bed hydrogenation cracking, it is characterized in that comprising organic facies, make active component as decentralized photo, a kind of sulphided state transition metal sodium rice particle by the water of surfactant parcel as decentralized medium, stable existence is in the aqueous phase of reversed phase micelle colloidal solution, wherein, organic facies is for comprising C
5Two components or the ternary mixture of above various linear paraffins, aromatic hydrocarbon, cycloalkane and linear paraffin, aromatic hydrocarbon or cycloalkane perhaps are a kind of or mixture each other in naphtha, benzinum, gasoline, diesel oil, the vacuum distillate; Surfactant is one or more in alkyl benzene sulphonate series, alkylbenzenesulfonate series, alkyl naphthalene sulfonic acid series, alkylnaphthalene sulfonate series, petroleum sulfonate, ligninsulfonate, organic aliphatic acid series, organic phosphate series, organic quaternary ammonium salt series, the organic quaternary alkylphosphonium salt series; The transition metal active component is the sulfide of one or more transition metals among group VIII, VIB and the VIIB in the periodic table of elements, it specifically consists of: the content of organic facies is 50～90m%, the content of water is 0.1～30m%, the content of aqueous phase transition metal active component is 8～45m%, and the content of surfactant is 0.01～10.0m%.
2. the reversed phase micelle nano catalyst that is used for dreg-oil suspension bed hydrogenation cracking according to claim 1, it is characterized in that, the transition metal active component is the sulphided state particle of one or more elements in Cu, Mn, Fe, Co, Ni, Cr, Mo, W, Zn, Sn or the Pb element, particle diameter is between 1nm～1000 μ m, and it is in the reversed phase micelle colloidal dispersion of decentralized medium that metal active constituent is evenly distributed on the organic facies.
3. preparation method who is used for the reversed phase micelle nano catalyst of dreg-oil suspension bed hydrogenation cracking, it is characterized in that the aqueous solution with the soluble metallic salt of one or more transition metals among group VIII, VIB and the VIIB in the periodic table of elements, under 10～80 ℃ of conditions, according to reversed phase micelle colloidal dispersion water content is that the addition of 0.1～30.0m% joins in the mixed solution of organic facies and surfactant, and wherein organic facies is C
5Above various linear paraffins, aromatic hydrocarbon, cycloalkane and linear paraffin, two components or the ternary mixture of aromatic hydrocarbon or cycloalkane, it perhaps is naphtha, benzinum, gasoline, diesel oil, a kind of or mixture each other in the vacuum distillate, surfactant is an alkyl benzene sulphonate series, alkylbenzenesulfonate series, alkyl naphthalene sulfonic acid series, alkylnaphthalene sulfonate series, petroleum sulfonate, ligninsulfonate, organic aliphatic acid series, organic phosphate series, organic quaternary ammonium salt series, in organic quaternary alkylphosphonium salt series one or more, the content of organic facies is 50～90m%, the content of surfactant is 0.01～10.0m%, stirred 0.5～1.5 hour, slowly add the vulcanizing agent aqueous solution then, reacted 0.5～1.5 hour, and be cooled to room temperature and promptly obtain required catalyst system.
4. the preparation method of reversed phase micelle nano catalyst according to claim 3 is characterized in that, the vulcanizing agent that is added is one or more in sodium salt, sylvite, ammonium salt or the thiosulfate of element sulphur.
5. the preparation method of reversed phase micelle nano catalyst according to claim 3 is characterized in that, the adding order of the catalyst and the vulcanizing agent aqueous solution can exchange.
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| CN103230806A (en) * | 2013-04-27 | 2013-08-07 | 中国石油大学(华东) | Super-dispersing nanometer catalyst for hydrocracking process of suspended bed |
| CN103480424A (en) * | 2013-09-22 | 2014-01-01 | 东北石油大学 | Preparation method and application of super dispersing catalyst for quality improvement and viscosity reduction of thickened oil |
| CN103525389A (en) * | 2012-07-02 | 2014-01-22 | 中国石油化工股份有限公司 | Nano-nickel catalyst for displacement of reservoir oil as well as preparation method thereof |
| CN109289932A (en) * | 2018-10-30 | 2019-02-01 | 中国石油大学(华东) | A kind of Ni-based high dispersive emulsion catalyst and its preparation method and application |
| CN111617757A (en) * | 2020-06-17 | 2020-09-04 | 中国石油大学(华东) | Preparation method and application of hybrid suspension bed solution catalyst |
| CN111644208A (en) * | 2020-06-17 | 2020-09-11 | 中国石油大学(华东) | Preparation method and application of oil-soluble suspension bed hydrogenation catalyst |
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- 2007-02-02 CN CN 200710013465 patent/CN101024186A/en active Pending
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| CN103525389A (en) * | 2012-07-02 | 2014-01-22 | 中国石油化工股份有限公司 | Nano-nickel catalyst for displacement of reservoir oil as well as preparation method thereof |
| CN103525389B (en) * | 2012-07-02 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of displacement of reservoir oil nano nickel catalyst and preparation method thereof |
| CN103230806A (en) * | 2013-04-27 | 2013-08-07 | 中国石油大学(华东) | Super-dispersing nanometer catalyst for hydrocracking process of suspended bed |
| CN103230806B (en) * | 2013-04-27 | 2015-11-18 | 中国石油大学(华东) | A kind of super-dispersed nano catalyst for hydrocracking process of suspended bed |
| CN103480424A (en) * | 2013-09-22 | 2014-01-01 | 东北石油大学 | Preparation method and application of super dispersing catalyst for quality improvement and viscosity reduction of thickened oil |
| CN109289932A (en) * | 2018-10-30 | 2019-02-01 | 中国石油大学(华东) | A kind of Ni-based high dispersive emulsion catalyst and its preparation method and application |
| CN111617757A (en) * | 2020-06-17 | 2020-09-04 | 中国石油大学(华东) | Preparation method and application of hybrid suspension bed solution catalyst |
| CN111644208A (en) * | 2020-06-17 | 2020-09-11 | 中国石油大学(华东) | Preparation method and application of oil-soluble suspension bed hydrogenation catalyst |
| 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 |
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