CN105498280A - Hydrophilic reversible solvent assisted oil-sand separation method - Google Patents
Hydrophilic reversible solvent assisted oil-sand separation method Download PDFInfo
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- CN105498280A CN105498280A CN201510999342.3A CN201510999342A CN105498280A CN 105498280 A CN105498280 A CN 105498280A CN 201510999342 A CN201510999342 A CN 201510999342A CN 105498280 A CN105498280 A CN 105498280A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/028—Flow sheets
- B01D11/0284—Multistage extraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/045—Separation of insoluble materials
Abstract
The invention relates to a hydrophilic reversible solvent assisted oil-sand separation method. A solid-liquid extraction organic solvent and a hydrophilic reversible solvent salt solution are simultaneously fed into an extraction device and are used for oil-sand extraction and separation, and asphalt separation is performed within the temperature range of 15-60 DEG C. A product discharge and a reagent recovery organic solvent are collected at the temperature of 70-200 DEG C through distillation, and organic matter left after distillation is an asphalt product. Residual sand left after oil-sand separation is washed with a small amount of water at normal temperature, and the residual sand product meets the clean discharge requirement. The recovery temperature of the used hydrophilic reversible solvent salt solution is 40-100 DEG C, the recovered hydrophilic reversible solvent and water can be recycled, energy is saved, and environmental protection is achieved. The asphalt recycling efficiency of the assisted oil-sand separation method is high and can be up to 99%, and the residual organic matter in the residual sand is little.
Description
Technical field
The present invention relates to a kind of separation method isolating asphalt component from oil-sand, belong to technical field of chemical separation, be specifically related to the post-processing approach adopting a kind of new additive agent secondary organic solvent extract and separate oil sands bitumen method and additive and residual solids.
Background technology
Oil-sand is a kind of natural minerals by sand grains, pitch, water, clay and a small amount of mineral composition, and outward appearance is black or pitchy.Within 1902, economize Late Cambrian at Canadian Alberta, be a kind of unconventional energy resource, global oil-sand resource amount is about 3.74 × 10
12bucket.
The oil-sand resource of Canada containing the whole world more than 75%, takes the lead in carrying out exploitation and the research of oil-sand in countries in the world, has the technology that the whole world is the most ripe at present.The oil-sand resource of China is mainly distributed in the ground such as Tarim, Xinjiang and Guizhou, not yet realizes suitability for industrialized production at present.The method of oil-sand exploitation mainly contains strip mining transformation and in-situ extraction, and the former is applicable to the oily placer mining that oil-sand ore deposit buried depth is less than 75 meters, and the latter is used for the exploitation that oil-sand ore deposit buried depth is greater than the oil-sand ore deposit of 75 meters.With regard to strip mining transformation, mainly contain thermokalite washing process, solvent extraction technology, thermal cracking process etc. several, current industrial use comparative maturity be thermokalite WATER-WASHING METHOD, oil-sand is first pulverized by this technology, send into mix and blend in heat alkali liquid again, then in mixed serum, pass into gas makes in pitch flotation, collects pitch and adds alkane dilution with after reducing its viscosity, is sent to refinery and carries out refining and obtain various oil product.This technical operation is simple, but there is following shortcoming and technical bottleneck: water consumption is large, energy consumption is high, tailings glass is extremely difficult, environmental pollution is serious, has been subjected to all over the world, especially the attention of mining area local resident and query.The oil sand separating method of searching environmental protection, economy, sustainable development is extremely urgent.
Solvent extraction is applicable to being separated of lipophile and hydrophily oil-sand due to it, and can eliminate emulsion to a certain extent, reduces the pollution to environment, obtains and pay attention to widely.Compared with traditional WATER-WASHING METHOD, adopt solvent to carry out extracting not containing sand in the oil obtained, and do not use water in overall process, reduce energy consumption, improve extraction efficiency, decrease the pollution to environment.Also there are some and have technical problem to be solved in traditional solvent extraction technology: efficient, economic solvent is not easy to obtain; Residue in solvent recovery difficulty in solid particles of sand larger etc.
Current many experts and scholars of having are devoted to research and use the extraction of additive secondary solvent, thus the fine sand reached in raising oil sands bitumen extraction yield, minimizing pitch is carried secretly and reduces the object of dissolvent residual in residual sand.CN102391185A (2012) reports the additive adopting ionic liquid as solvent extraction oil-sand pitch, pitch extraction yield can be improved, but because ionic liquid involves great expense, although can be reclaimed by the mode of transpiring moisture, its loss during the course still limits its commercial Application.US4929341 (1990) reports ammonium sulfate, acetone, sulfuric acid etc. can promote organic solvent (tetrachloro-ethylene, carbon tetrachloride, benzinum, toluene, the benzene etc.) effect of extracting to oil-sand, but this technology need extract 4 hours can obtain better effects.Comprehensive forefathers are about the patented technology using additive secondary solvent abstraction technique to be separated oil-sand, the common problem run into is exactly the process problem about microactuator suspension particle in residual sand after extraction and extract, some technology can reach higher extraction efficiency, but the problem of solvent recovery in residue cannot be solved, what have can solve solvent recovery problem in residue, but economic cost is too high, cannot industrializing implementation, these are also the reasons why solvent extraction technology really cannot drop into industrial application up to now always; Therefore, solvent extraction will obtain industrialization and use, and must solve to residue in solvent and the organic recovery of pitch and additive in solid and reclaim problem, and whole process economics, environmental protection the synthtic price index such as running.
The reversible tertiary amine of hydrophily is a kind of novel intelligent solvent occurred in recent years.This tertiary amine can be dissolved in water by generating tertiary amine bicarbonate under water and carbon dioxide existence condition, and carbon dioxide can be discharged under the condition heated or pass into the inert gases such as nitrogen, with water stratification, thus be reduced to hydrophobic tertiary amine, achieve the process that hydrophily is reversible.Based on current research, in traditional organic solvent, introduce the reversible tertiary amine auxiliary extraction of hydrophily, the effect of separation is better, and the organic solvent simultaneously used and the easier recovery and reuse of tertiary amine, prospects for commercial application is boundless.
Summary of the invention
The object of the invention is to study a kind ofly to have fewer environmental impacts, energy consumption is low, water consumption is few, the simple and separation method of efficient extraction oil-sand medium pitch component.The method takes the asphalt component in hydrophily reversible tertiary ammonium salt solution secondary organic solvent separation oil-sand, by coordinating the corresponding technique in the present invention, the temperature of 15-60 DEG C, effectively can be separated by the asphalt component in oil-sand under normal pressure.
The technical solution adopted for the present invention to solve the technical problems is:
Organic solvent is separated a method for oil-sand, adds the reversible solvent of hydrophily as auxiliary additive during organic solvent extraction oil-sand.
And, the reversible solvent of described hydrophily is: can be dissolved in water by generating corresponding bicarbonate under water and carbon dioxide existence condition, and carbon dioxide can be discharged under the condition heated or pass into the inert gases such as nitrogen, with water stratification, be reduced to hydrophobic containing N solvent, what achieve the reversible process of hydrophily contains N organic matter.
And, in the reversible solvent of described hydrophily, tertiary amines is triethylamine, N, N-dimethyl cyclohexyl amine, N, N-dimethyl benzylamine, N, N-dimethyl butylamine, N-ethylpiperidine, N-methyl-di-n-propylamine, N-butyl pyrrolidine, N, N-diethyl butylamine, N, N-dimethylhexylamine, N, N-phenpromethamine, N, N, N '-triethyl group penta amidine, N, N, the own amidine of N '-tributyl, diisopropyl ethanolamine, 4,4-diethoxy-N, N-dimethyl butylamine, 4-diethylin ethyl butyrate, 5-dipropyl amido-2 pentanone, dibutylamino ethanol; Secondary amine class is di-n-propylamine, 3-sec-butylamine guanidine-acetic acid propyl ester, 3-isopropylamine base propyl butyrate, 3-sec-butylamine base propyl propionate, N-propyl group sec-butylamine, di-sec-butyl amine.
And described organic solvent is the single organic solvent of benzene,toluene,xylene or Reformed Gasoline, or be acetone-alkanes complex solvent, ethyl acetate-alkanes complex solvent.
And described acetone-alkanes complex solvent is acetone-normal heptane, acetone-n-hexane, acetone-cycloalkane, acetone-petroleum ether or acetone-naphtha.
And described ethyl acetate-alkanes complex solvent is ethyl acetate-normal heptane, ethyl acetate-hexane, ethyl acetate-cycloalkane, ethyl acetate-light petrol or ethyl acetate-naphtha.
And raw material amine and the water volume ratio of the reversible lyonium salt solution of described hydrophily are 1:1-10; The 1-5L/kg that the reversible lyonium salt solution interpolation volume of hydrophily and oil-sand mass ratio are; Organic solvent volume and oil-sand mass ratio are 1-12 times of L/kg.
Organic solvent capable of circulation is separated a method for oil-sand, and step is as follows:
(1) the reversible lyonium salt solution of synthesis hydrophilic;
(2) hybrid extraction: organic solvent and the reversible lyonium salt solution of hydrophily enter extraction equipment simultaneously, carry out oil-sand extract and separate; The 1-5L/kg that the reversible lyonium salt solution interpolation volume of hydrophily and oil-sand mass ratio are; Organic solvent volume and oil-sand mass ratio are 1-12 times of L/kg;
(3) Separation of Solid and Liquid: left standstill by the mixing solid-liquid after extraction, isolated upper phase organic solvent/coal tar mixture is separated, solvent recovery uses, coal tar refining;
(4) washed by the grains of sand+ammonium salt solution of standing rear lower, the residual sand after washing is discharged by the bottom of still;
(5) ammonium salt solution is passed into reactor, pump into air and heat 40-100 DEG C simultaneously, reacted recovery amine and recycle-water, recycle, and completes overall circular response.
(6) the recovery of ammonium salt and water: the ammonium salt weak solution left standstill by secondary in the ammonium salt solution separated in the middle part of groove and washing kettle passes into reactor, passes into air in reactor, reacted recovery amine and recycle-water, and unreacted air is discharged from still top.
And (4) described step leaves standstill after the grains of sand+ammonium salt solution of rear lower carries out reextraction, then washes; Described reextraction step is: lower floor's ammonium salt solution+grains of sand are carried out secondary extraction, then adds the organic solvent extraction of the quality such as 1-3 times of solid, leaves standstill after extraction; By upper organic phase through step process (3), the grains of sand+ammonium salt solution of bottom is washed again.
And described organic solvent is the single organic solvent of benzene,toluene,xylene or Reformed Gasoline, or be acetone-alkanes complex solvent, ethyl acetate-alkanes complex solvent.
The invention has the beneficial effects as follows:
1, reversible for hydrophily lyonium salt solution is applied to the separation of oil sands bitumen by this method, jointly forms environment-friendly type Diversity release agent with organic solvent; Hybrid separation agent improves bitumen recovery rate, can reach 99%, and in residual sand, residual organic matter is few; The a small amount of washing of residual sand after extraction can remove the ammonium salt on grains of sand surface, energy-saving and water-saving environmental protection.
2, the present invention is by flow process reasonable in design, make the reversible solvent of hydrophily and water can realize recycling in whole process, and operating condition is gentle, greatly cost-saving.
3, the present invention adds organic solvent extract in oil-sand separation, the oil sands bitumen oil extracted does not need additionally to add diluent and is diluted by pitch, directly extract is delivered to refinery, then isolates solvent recycling, decrease intermediate link, save intermediary operation cost.
4, the present invention advises that the method adopting multistage (1-2 level) to extract extracts oil-sand, not only increases extraction efficiency; And extraction process can continued operation, and good stability, ensure that the continuity of production, improve production efficiency.
Accompanying drawing explanation
Fig. 1: the process chart of separation method of the present invention.
Stock number: 1. amine, 2. water, 3. carbon dioxide, 4. ammonium salt solution, 5. circulating solvent, 6. oil-sand or oil shale mine, 7. organic solvent/ammonium salt solution/grains of sand mixed serum I, 8. ammonium salt solution+grains of sand, 9. solvent/coal tar mixture, 10. circulating solvent, 11. organic solvents/ammonium salt solution/grains of sand mixed serum II, 12. solvents/coal tar mixture, 13. grains of sand+a small amount of ammonium salt solution, 14. ammonium salt solutions, 15. fresh waters, the grains of sand after 16. washings, 17. ammonium salt weak solutions, 18. air, 19. reclaim amine, 20. recycle-waters, 21. solvents/coal tar mixture, product after 22. refinings, 23. recycling design.
Device is numbered: 24. amine recycling cans, 25. water recovery tanks, 26. reactor I, 27. one-level extraction kettles, 28. circulating solvent tanks, 29. one-levels leave standstill groove, 30. secondary extraction kettles, and 31. secondarys leave standstill groove, 32. washing kettles, 33. reactors II, 34. solvents/coal tar storage tank, 35. refined units.
Detailed description of the invention
Below in conjunction with accompanying drawing, also by specific embodiment, the invention will be further described, and following examples are descriptive, are not determinate, can not limit protection scope of the present invention with this.
The invention provides the reversible solvent of a kind of hydrophily is separated the auxiliary additive of oil-sand application as organic solvent, the reversible solvent of described hydrophily is triethylamine, N, N-dimethyl cyclohexyl amine, N, N-dimethyl benzylamine and anyly to meet: can by generating bicarbonate and be dissolved in water under water and carbon dioxide existence condition, and carbon dioxide can be discharged under the condition heated or pass into the inert gases such as nitrogen, with water stratification, be reduced to hydrophobic amine, achieve tertiary amine or the secondary amine of the reversible process of hydrophily.Organic solvent can be the single organic solvent of benzene,toluene,xylene or Reformed Gasoline, or is acetone-alkanes complex solvent, ethyl acetate-alkanes complex solvent.
Described acetone-alkanes complex solvent is acetone-normal heptane, acetone-n-hexane, acetone-cycloalkane, acetone-petroleum ether or acetone-naphtha.Described ethyl acetate-alkanes complex solvent is ethyl acetate-normal heptane, ethyl acetate-hexane, ethyl acetate-cycloalkane, ethyl acetate-light petrol or ethyl acetate-naphtha.
According to the guidance of above-mentioned application, present invention also offers the method for a kind of hydrophily reversible solvent secondary organic solvent extraction oil sand separation, this separation method with an organic solvent extracts oil-sand, the reversible solvent of hydrophily not only can improve bitumen recovery rate as additive, effectively can also reduce the fine content reclaimed in pitch, reduce the solvent in residual sand simultaneously, additive can recycle, decrease environmental pollution, save solvent materials, improve comprehensive utilization of energy rate, concrete steps are as follows:
(1) the raw material tertiary amine of the reversible lyonium salt solution of synthesis hydrophilic and water volume ratio are 1:1-10; (2) the reversible lyonium salt solution of hydrophily adds the 1-5L/kg that volume and oil-sand mass ratio are; Organic solvent volume and oil-sand mass ratio are 1-12 times of L/kg; (3) leaching organic solvent and the reversible lyonium salt solution of hydrophily enter extraction equipment simultaneously, and for oil-sand extract and separate, pitch separation temperatures scope is carry out at 15-60 DEG C; (4) product discharge and reagent reclaim organic solvent at 70-200 DEG C through distillation collection, and distillation residual organic substances is asphaltic products; (5) the residual sand after oil-sand separation and hydrophily reversible lyonium salt solution normal temperature are through a small amount of washing, and residual sand product reaches clean discharging; (6) the hydrophily reversible lyonium salt solution recovered temperature after using is 40-100 DEG C, and the amine after recovery and water can be recycled.
The present invention adding and recovery feature also according to reversible tertiary amine auxiliary additive, equipment and the process matched therewith of the closed circulation of a set of basic realization are provided, are described as follows:
The core apparatus of oil-sand solvent extraction and separation is the one-level extraction kettle 27 with mechanical agitator and the secondary extraction kettle 31 of sealing.The reversible lyonium salt solution of hydrophily synthesizes in reactor I 26.One-level extraction kettle 27 plays main extract and separate effect, and secondary extraction kettle 30 is in order to pitch residual in the residual sand after being processed by one-level extraction kettle 27 continues to extract; The residual sand separated from secondary extraction tank 30, because of containing a small amount of ammonium salt solution, can not directly discharge, and discharges after adopting washing kettle 32 to wash it in the present invention again.Standing groove 29,31 liquid phase be out connected with secondary extraction kettle 30 from one-level extraction kettle 27 is sent to refined unit; Leave standstill the reversible lyonium salt solution of the isolated hydrophily of groove 31 from secondary and generate amine and water through reactor II 33, recycle, decrease environmental pollution, saved solvent materials, improve comprehensive utilization of energy rate.
The concrete operation step of process implementing:
(1) the synthesis of hydrophily reversible lyonium salt solution: amine 1 and water 2 pass into mechanical agitator reactor I 26 from amine recycling can 24 and water recovery tank 25 with same flow respectively, be uniformly mixed, carbon dioxide 3 autoreaction still middle and lower part passes into, contact with liquid phase in still and react, unreacted carbon dioxide is discharged from still top blast pipe, stop reaction after ventilation 1h, the synthetic reversible lyonium salt solution 4 of hydrophily is passed into one-level extraction kettle 27;
(2) hybrid extraction: the oil-sand/oil shale mine 6 from mining area sends into one-level extraction kettle 27 with at the reversible lyonium salt solution 4 of a certain proportion of hydrophily in still and circulating solvent (extraction organic solvent) 5 in 25-100 DEG C, after carrying out mix and blend extraction 2-60min, organic solvent/ammonium salt solution/sand grains mixed serum I 7 feeding one-level is left standstill groove 29 and leaves standstill, thus reaches Separation of Solid and Liquid object;
(3) Separation of Solid and Liquid: coagulation ammonium salt solution+grains of sand 8 that one-level to leave standstill bottom groove 29 are out delivered in secondary extraction kettle 30, add the circulating solvent of the quality such as 1-3 times of solid at 25-100 DEG C, carry out washing extraction 2-60min, the organic solvent/ammonium salt solution/sand grains mixed serum II 11 of extraction is also sent into secondary and is left standstill groove 31;
(4) solvent/coal tar mixture is separated: liquid phase solvent/coal tar mixture 9,12 isolated in two-stage defecator 30,31 is delivered to refinery unit 35 and carries out solvent/coal tar and be separated and coal tar refining, is separated and the recycling design 23 that obtains is delivered to circulating solvent tank 28 and recycles from refinery unit 35; Solvent/coal tar mixture 21 can obtain the product 22 after refining after refinery unit 35;
(5) the grains of sand+a small amount of ammonium salt solution 13 that secondary leaves standstill bottom groove 31 is delivered in washing kettle 32 and washes, and the residual sand 16 after washing is discharged by the bottom of still;
(6) the recovery of ammonium salt and water: secondary is left standstill the ammonium salt solution 14 separated in the middle part of groove 31 and pass into reactor II 33 with the ammonium salt weak solution 17 in washing kettle 32, air 18 to be passed into by still middle and lower part through pump and contacts with reactant liquor in still, pass in reacting kettle jacketing and be steam heated to 40-100 DEG C, reacted recovery amine 19 and recycle-water 20 pass into amine recycling can 24 and water recovery tank 25 respectively, and unreacted air is discharged from still top.
This method adopts additive recycling method, decreases environmental pollution; Adopt multistage (1-2 level) to extract, with the use of mechanical settling tank, ensure that production is able to continuously, improve extraction efficiency and productive rate, also save solvent; The solid particle produced in extraction process is divided into two parts process, improves treatment effect, decrease environmental pollution, take full advantage of the energy; Adopt suspension isolation technics to remove the microparticle be suspended in extract, reduce operational load; Adopt WATER-WASHING METHOD process microparticle, can effective use of energy sources, emissions reduction pressure.
Below, the present invention's following examples are described, but are not limited to following examples.
Embodiment 1:
Several different hydrophilic reversible tertiary amine secondary solvent extraction oil sands bitumen method.
Adopt three kinds of reversible solvents of hydrophily respectively: triethylamine, N, N-dimethyl cyclohexyl amine, N, N-dimethyl benzylamine, N-ethylpiperidine.Toluene is extractant.
The reversible tertiary amine of 5L hydrophily and 5L water pass into reactor I 26 from amine recycling can 24 and water recovery tank 25 respectively, open reactor mechanical agitation, rotating speed 300rpm, open carbon dioxide valve, pass into carbon dioxide from reactor middle and lower part, gas speed is 5L/min, closing carbon dioxide gas valve after ventilatory response 1h, stop stirring, reactant liquor passes into one-level extraction kettle 27.Oil-sand 5kg sends into one-level extraction kettle 27 and mixes with tertiary ammonium salt solution and 15L toluene, at 25 DEG C, carry out mix and blend extraction 25min, reduce mixing speed, leave standstill after groove 29 solid-liquor separation, upper strata organic solvent to be sent into mutually through one-level and be sent to solvent/coal tar storage tank 34 mutually and store, the residual sand and the tertiary ammonium salt solution that one-level are left standstill bottom in 29 grooves are sent in secondary extraction kettle 30 simultaneously, add the circulating solvent of the quality such as 3 times of solids at 25 DEG C, carry out washing extraction 25min, then enter secondary and leave standstill groove 31, organic solvent is sent to solvent/coal tar storage tank 34 mutually and stores, tertiary ammonium salt solution sends into reactor II 33, secondary leaves standstill residual sand bottom groove 31 and sends into washing kettle 32, in still, add 5L water simultaneously, stir washing 10min, 20min is left standstill after washing, the residual sand in bottom is discharged by discharging opening, upper aqueous phase delivers to reactor II 33.In reactor II 33, tertiary ammonium salt solution passes into air at 70 DEG C, and gas speed is 5L/min, and leave standstill 20min after ventilation 1h, upper organic phase delivers to reversible solvent recovery tank 1, and lower floor's aqueous phase delivers to water (or alcohol) recycling can 2.Solvent/coal tar the mixture 21 being stored in solvent/coal tar storage tank 34 is sent to refinery's refined unit 35 through oil pipeline.
Several different hydrophilic of table 1 reversible tertiary amine assisting oil-sand extraction bitumen recovery rate
Embodiment 2:
Several different hydrophilic reversible secondary amine secondary solvent extraction oil sands bitumen method.
Adopt three kinds of reversible solvents of hydrophily respectively: di-n-propylamine, 3-sec-butylamine guanidine-acetic acid propyl ester, N-propyl group sec-butylamine, di-sec-butyl amine.Toluene is extractant.
The reversible secondary amine of 5L hydrophily and 5L water pass into reactor I 26 from amine recycling can 24 and water recovery tank 25 respectively, open reactor mechanical agitation, rotating speed 300rpm, open carbon dioxide valve, pass into carbon dioxide from reactor middle and lower part, gas speed is 5L/min, closing carbon dioxide gas valve after ventilatory response 1h, stop stirring, reactant liquor passes into one-level extraction kettle 27.Oil-sand 5kg sends into one-level extraction kettle 27 and mixes with tertiary ammonium salt solution and 15L toluene, at 25 DEG C, carry out mix and blend extraction 25min, reduce mixing speed, leave standstill after groove 29 solid-liquor separation, upper strata organic solvent to be sent into mutually through one-level and be sent to solvent/coal tar storage tank 34 mutually and store, the residual sand and the tertiary ammonium salt solution that one-level are left standstill bottom in 29 grooves are sent in secondary extraction kettle 30 simultaneously, add the circulating solvent of the quality such as 3 times of solids at 25 DEG C, carry out washing extraction 25min, then enter secondary and leave standstill groove 31, organic solvent is sent to solvent/coal tar storage tank 34 mutually and stores, tertiary ammonium salt solution sends into reactor II 33, secondary leaves standstill residual sand bottom groove 31 and sends into washing kettle 32, in still, add 5L water simultaneously, stir washing 10min, 20min is left standstill after washing, the residual sand in bottom is discharged by discharging opening, upper aqueous phase delivers to reactor II 33.In reactor II 33, tertiary ammonium salt solution passes into air at 70 DEG C, and gas speed is 5L/min, and leave standstill 20min after ventilation 1h, upper organic phase delivers to reversible solvent recovery tank 1, and lower floor's aqueous phase delivers to water (or alcohol) recycling can 2.Solvent/coal tar the mixture 21 being stored in solvent/coal tar storage tank 34 is sent to refinery's refined unit 35 through oil pipeline.
Several different hydrophilic of table 2 reversible secondary amine assisting oil-sand extraction bitumen recovery rate
Embodiment 3:
The hydrophily reversible tertiary amine assisting oil-sand separation method of several different organic solvents.
Adopt six kinds of organic solvents to extract respectively, single organic solvent adopts toluene, dimethylbenzene; Double solvents adopts first benzene and heptane volume ratio 1:3; Acetone and normal heptane volume ratio 1:3; The solvent of ethyl acetate and normal heptane volume ratio 1:3.
5L triethylamine and 5L water pass into reactor I 26 from amine recycling can 24 and water recovery tank 25 respectively, open reactor mechanical agitation, rotating speed 300rpm, open carbon dioxide valve, pass into carbon dioxide from reactor middle and lower part, gas speed is 5L/min, closing carbon dioxide gas valve after ventilatory response 1h, stop stirring, reactant liquor passes into one-level extraction kettle 27.Oil-sand 5kg sends into one-level extraction kettle 27 and mixes with tertiary ammonium salt solution and 15L solvent, at 25 DEG C, carry out mix and blend extraction 25min, reduce mixing speed, leave standstill after groove 29 solid-liquor separation, upper strata organic solvent to be sent into mutually through one-level and be sent to solvent/coal tar storage tank 34 mutually and store, the residual sand and the tertiary ammonium salt solution that one-level are left standstill bottom in 29 grooves are sent in secondary extraction kettle 30 simultaneously, add the circulating solvent of the quality such as 3 times of solids at 25 DEG C, carry out washing extraction 25min, then enter secondary and leave standstill groove 31, organic solvent is sent to solvent/coal tar storage tank 34 mutually and stores, tertiary ammonium salt solution sends into reactor II 33, secondary leaves standstill residual sand bottom groove 31 and sends into washing kettle 32, in still, add 5L water simultaneously, stir washing 10min, 20min is left standstill after washing, the residual sand in bottom is discharged by discharging opening, upper aqueous phase delivers to reactor II 33.In reactor II 33, tertiary ammonium salt solution passes into air at 70 DEG C, and gas speed is 5L/min, and leave standstill 20min after ventilation 1h, upper organic phase delivers to tertiary amine recycling can 1, and lower floor's aqueous phase delivers to water recovery tank 2.Solvent/coal tar the mixture 21 being stored in solvent/coal tar storage tank 34 is sent to refinery's refined unit 35 through oil pipeline.
The hydrophily reversible tertiary amine assisting oil-sand extraction bitumen recovery rate of several different organic solvents of table 3
Embodiment 4:
Several different hydrophilic reversible tertiary amine consumption assisting oil-sand separation method.
Organic solvent adopts ethyl acetate: normal heptane=1:3, the reversible tertiary amine consumption of hydrophily and oil-sand ratio (V/W) are respectively 1:2,1:1,2:1,3:1,4:1.
5L triethylamine and 5L water pass into reactor I 26 from amine recycling can 24 and water recovery tank 25 respectively, open reactor mechanical agitation, rotating speed 300rpm, open carbon dioxide valve, pass into carbon dioxide from reactor middle and lower part, gas speed is 5L/min, closing carbon dioxide gas valve after ventilatory response 1h, stop stirring, reactant liquor passes into one-level extraction kettle 27.Oil-sand 5kg sends into the tertiary ammonium salt solution of one-level extraction kettle 27 and certain volume and 15L solvent mixes, at 25 DEG C, carry out mix and blend extraction 25min, reduce mixing speed, leave standstill after groove 29 solid-liquor separation, upper strata organic solvent to be sent into mutually through one-level and be sent to solvent/coal tar storage tank 34 mutually and store, the residual sand and the tertiary ammonium salt solution that one-level are left standstill bottom in 29 grooves are sent in secondary extraction kettle 30 simultaneously, add the circulating solvent of the quality such as 3 times of solids at 25 DEG C, carry out washing extraction 25min, then enter secondary and leave standstill groove 31, organic solvent is sent to solvent/coal tar storage tank 34 mutually and stores, tertiary ammonium salt solution sends into reactor II 33, secondary leaves standstill residual sand bottom groove 31 and sends into washing kettle 32, in still, add 5L water simultaneously, stir washing 10min, 20min is left standstill after washing, the residual sand in bottom is discharged by discharging opening, upper aqueous phase delivers to reactor II 33.In reactor II 33, tertiary ammonium salt solution passes into air at 70 DEG C, and gas speed is 5L/min, and leave standstill 20min after ventilation 1h, upper organic phase delivers to tertiary amine recycling can 1, and lower floor's aqueous phase delivers to water recovery tank 2.Solvent/coal tar the mixture 21 being stored in solvent/coal tar storage tank 34 is sent to refinery's refined unit 35 through oil pipeline.
Several different hydrophilic of table 4 reversible tertiary amine consumption assisting oil-sand extraction bitumen recovery rate
Embodiment 5:
The hydrophily reversible tertiary amine assisting oil-sand separation method of several consumption of organic solvent.
Organic solvent adopts ethyl acetate: normal heptane=1:3, hydrophily reversible tertiary amine aqueous solution 5L, consumption of organic solvent and oil-sand ratio (V/W) are respectively 2:1,3:1,4:1,5:1,6:1.
5L triethylamine and 5L water pass into reactor I 26 from amine recycling can 24 and water recovery tank 25 respectively, open reactor mechanical agitation, rotating speed 300rpm, open carbon dioxide valve, pass into carbon dioxide from reactor middle and lower part, gas speed is 5L/min, closing carbon dioxide gas valve after ventilatory response 1h, stop stirring, reactant liquor passes into one-level extraction kettle 27.Oil-sand 5kg sends into one-level extraction kettle 27 and mixes with the solvent of tertiary ammonium salt solution and certain volume, at 25 DEG C, carry out mix and blend extraction 25min, reduce mixing speed, leave standstill after groove 29 solid-liquor separation, upper strata organic solvent to be sent into mutually through one-level and be sent to solvent/coal tar storage tank 34 mutually and store, the residual sand and the tertiary ammonium salt solution that one-level are left standstill bottom in 29 grooves are sent in secondary extraction kettle 30 simultaneously, add the circulating solvent of certain volume at 25 DEG C, carry out washing extraction 25min, then enter secondary and leave standstill groove 31, organic solvent is sent to solvent/coal tar storage tank 34 mutually and stores, tertiary ammonium salt solution sends into reactor II 33, secondary leaves standstill residual sand bottom groove 31 and sends into washing kettle 32, in still, add 5L water simultaneously, stir washing 10min, 20min is left standstill after washing, the residual sand in bottom is discharged by discharging opening, upper aqueous phase delivers to reactor II 33.In reactor II 33, tertiary ammonium salt solution passes into air at 70 DEG C, and gas speed is 5L/min, and leave standstill 20min after ventilation 1h, upper organic phase delivers to tertiary amine recycling can 1, and lower floor's aqueous phase delivers to water recovery tank 2.Solvent/coal tar the mixture 21 being stored in solvent/coal tar storage tank 34 is sent to refinery's refined unit 35 through oil pipeline.
Several solvent load of table 5 assists hydrophily reversible tertiary amine oil-sand extraction bitumen recovery rate
Embodiment 6:
The hydrophily reversible tertiary amine assisting oil-sand separation method of several different temperatures.
Organic solvent adopts ethyl acetate: normal heptane=1:3, hydrophily reversible tertiary amine aqueous solution 5L, consumption of organic solvent 15L, temperature is respectively 15 DEG C, 25 DEG C, 35 DEG C, 45 DEG C.
5L triethylamine and 5L water pass into reactor I 26 from tertiary amine recycling can 24 and water recovery tank 25 respectively, open reactor mechanical agitation, rotating speed 300rpm, open carbon dioxide valve, pass into carbon dioxide from reactor middle and lower part, gas speed is 5L/min, closing carbon dioxide gas valve after ventilatory response 1h, stop stirring, reactant liquor passes into one-level extraction kettle 27.Oil-sand 5kg sends into one-level extraction kettle 27 and mixes with tertiary ammonium salt solution and 15L solvent, under uniform temperature, carry out mix and blend extraction 25min, reduce mixing speed, leave standstill after groove 29 solid-liquor separation, upper strata organic solvent to be sent into mutually through one-level and be sent to solvent/coal tar storage tank 34 mutually and store, the residual sand and the tertiary ammonium salt solution that one-level are left standstill bottom in 29 grooves are sent in secondary extraction kettle 30 simultaneously, add the circulating solvent of the quality such as 3 times of solids under uniform temperature, carry out washing extraction 25min, then enter secondary and leave standstill groove 31, organic solvent is sent to solvent/coal tar storage tank 34 mutually and stores, tertiary ammonium salt solution sends into reactor II 33, secondary leaves standstill residual sand bottom groove 31 and sends into washing kettle 32, in still, add 5L water simultaneously, stir washing 10min, 20min is left standstill after washing, the residual sand in bottom is discharged by discharging opening, upper aqueous phase delivers to reactor II 33.In reactor II 33, tertiary ammonium salt solution passes into air at 70 DEG C, and gas speed is 5L/min, and leave standstill 20min after ventilation 1h, upper organic phase delivers to tertiary amine recycling can 1, and lower floor's aqueous phase delivers to water recovery tank 2.Solvent/coal tar the mixture 21 being stored in solvent/coal tar storage tank 34 is sent to refinery's refined unit 35 through oil pipeline.
The hydrophily reversible tertiary amine assisting oil-sand extraction bitumen recovery rate of several temperature of table 6
Claims (10)
1. organic solvent is separated a method for oil-sand, it is characterized in that: add hydrophily reversible solvent during organic solvent extraction oil-sand as auxiliary additive.
2. organic solvent according to claim 1 is separated the method for oil-sand, it is characterized in that: the reversible solvent of described hydrophily is: can be dissolved in water by generating corresponding bicarbonate under water and carbon dioxide existence condition, and carbon dioxide can be discharged under the condition heated or pass into the inert gases such as nitrogen, with water stratification, be reduced to hydrophobic containing N solvent, what achieve the reversible process of hydrophily contains N organic matter.
3. organic solvent according to claim 1 is separated the method for oil-sand, it is characterized in that: in the reversible solvent of described hydrophily, tertiary amines is triethylamine, N, N-dimethyl cyclohexyl amine, N, N-dimethyl benzylamine, N, N-dimethyl butylamine, N-ethylpiperidine, N-methyl-di-n-propylamine, N-butyl pyrrolidine, N, N-diethyl butylamine, N, N-dimethylhexylamine, N, N-phenpromethamine, N, N, N '-triethyl group penta amidine, N, N, the own amidine of N '-tributyl, diisopropyl ethanolamine, 4, 4-diethoxy-N, N-dimethyl butylamine, 4-diethylin ethyl butyrate, 5-dipropyl amido-2 pentanone, dibutylamino ethanol, secondary amine class is di-n-propylamine, 3-sec-butylamine guanidine-acetic acid propyl ester, 3-isopropylamine base propyl butyrate, 3-sec-butylamine base propyl propionate, N-propyl group sec-butylamine, di-sec-butyl amine.
4. organic solvent according to claim 1 is separated the method for oil-sand, it is characterized in that: described organic solvent is the single organic solvent of benzene,toluene,xylene or Reformed Gasoline, or be acetone-alkanes complex solvent, ethyl acetate-alkanes complex solvent.
5. organic solvent according to claim 4 is separated the method for oil-sand, it is characterized in that: described acetone-alkanes complex solvent is acetone-normal heptane, acetone-n-hexane, acetone-cycloalkane, acetone-petroleum ether or acetone-naphtha.
6. organic solvent according to claim 4 is separated the method for oil-sand, it is characterized in that: described ethyl acetate-alkanes complex solvent is ethyl acetate-normal heptane, ethyl acetate-hexane, ethyl acetate-cycloalkane, ethyl acetate-light petrol or ethyl acetate-naphtha.
7. organic solvent according to claim 1 is separated the method for oil-sand, it is characterized in that: raw material amine and the water volume ratio of the reversible lyonium salt solution of described hydrophily are 1:1-10; The 1-5L/kg that the reversible lyonium salt solution interpolation volume of hydrophily and oil-sand mass ratio are; Organic solvent volume and oil-sand mass ratio are 1-12 times of L/kg.
8. organic solvent capable of circulation is separated a method for oil-sand, it is characterized in that step is as follows:
(1) the reversible lyonium salt solution of synthesis hydrophilic;
(2) hybrid extraction: organic solvent and the reversible lyonium salt solution of hydrophily enter extraction equipment simultaneously, carry out oil-sand extract and separate; The 1-5L/kg that the reversible lyonium salt solution interpolation volume of hydrophily and oil-sand mass ratio are; Organic solvent volume and oil-sand mass ratio are 1-12 times of L/kg;
(3) Separation of Solid and Liquid: left standstill by the mixing solid-liquid after extraction, isolated upper phase organic solvent/coal tar mixture is separated, solvent recovery uses, coal tar refining;
(4) washed by the grains of sand+ammonium salt solution of standing rear lower, the residual sand after washing is discharged by the bottom of still;
(5) ammonium salt solution is passed into reactor, pump into air and heat 40-100 DEG C simultaneously, reacted recovery amine and recycle-water, recycle, and completes overall circular response.
(6) the recovery of ammonium salt and water: the ammonium salt weak solution left standstill by secondary in the ammonium salt solution separated in the middle part of groove and washing kettle passes into reactor, passes into air in reactor, reacted recovery amine and recycle-water, and unreacted air is discharged from still top.
9. organic solvent capable of circulation according to claim 8 is separated the method for oil-sand, it is characterized in that: after the grains of sand+ammonium salt solution that (4) described step leaves standstill rear lower carries out reextraction, then wash; Described reextraction step is: lower floor's ammonium salt solution+grains of sand are carried out secondary extraction, then adds the organic solvent extraction of the quality such as 1-3 times of solid, leaves standstill after extraction; By upper organic phase through step process (3), the grains of sand+ammonium salt solution of bottom is washed again.
10. organic solvent capable of circulation according to claim 8 is separated the method for oil-sand, it is characterized in that: described organic solvent is the single organic solvent of benzene,toluene,xylene or Reformed Gasoline, or be acetone-alkanes complex solvent, ethyl acetate-alkanes complex solvent.
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| CN107760353A (en) * | 2017-11-14 | 2018-03-06 | 天津大学 | It is a kind of that the oily method separated admittedly is carried out using Reversible extract solvent |
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