CN106010621B - A kind of separation and recovery method and system rich in carbonate heavy oil field - Google Patents

A kind of separation and recovery method and system rich in carbonate heavy oil field Download PDF

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CN106010621B
CN106010621B CN201610298740.7A CN201610298740A CN106010621B CN 106010621 B CN106010621 B CN 106010621B CN 201610298740 A CN201610298740 A CN 201610298740A CN 106010621 B CN106010621 B CN 106010621B
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solid
liquid
separation
heavy oil
oil
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CN106010621A (en
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何林
隋红
李鑫钢
丛山
许长春
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Tianjin University
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Tianjin University
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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
    • 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
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials

Abstract

The present invention is a kind of separation and recovery method and system rich in carbonate heavy oil field, the heavy oil resources of carbonate containing mineral matter, such as oil-sand, oil shale, ground sludge, mixed in any case with the solution and chemical addition agent configured, react, mineral matter in heavy oil field is dissolved, so as to reach the target for separating mink cell focus with mineral grain.Mink cell focus after separation is handled by following process, further except the moisture and solid particle of deentrainment, obtains clean hydrocarbon class composition；And waste liquid caused by process and mineral deposits then carry out that processing is separately recovered, harmless discharge is finally realized.This not only effectively extracts mink cell focus from ore deposit, and greatly saves the energy, realizes energy-conservation, the emission reduction production purpose of normal temperature extraction or recovery mink cell focus.

Description

A kind of separation and recovery method and system rich in carbonate heavy oil field
Technical field
The present invention relates to a kind of separation method that mink cell focus is isolated from rich in carbonate heavy oil field, belongs to chemical industry point From and reaction engineering technical field, and in particular to the methods of broken, reaction, sedimentation, filtering, distillation, crystallization.
Background technology
Heavy oil field (e.g., oil-sand, oil shale, landing oil, greasy filth etc.) be it is a kind of by mink cell focus (or pitch), it is the grains of sand, viscous The complex mixture of native and a small amount of water composition.Because its processing is huge, a kind of petroleum resources of standby have been increasingly becoming.Using oil-sand as Example, its proved reserves account for 1/3rd or so of existing petroleum resources total amount, and prior art recoverable reserves is about 651,000,000,000 barrels, The ground such as Canada, Venezuela, the U.S., Russia, Indonesia and China are mainly distributed on, are a kind of very promising oil replacements The energy.
The exploitation of oil-sand can be divided into strip mining transformation and in-situ extraction according to its own physicochemical property and geological conditions.For Canadian moisturizing type oil-sand, it is industrial mainly using thermokalite washing process to oil-sand when mineral products buried depth is less than 75 meters Separated；And when oil-sand ore deposit buried depth is more than 75 meters, then using in-situ extraction method, such as to bottom inject heat steaming Vapour, hot solvent etc..However, for glossy property oil-sand, the nothing if Utah, USA oil-sand, Indonesia's oil-sand and Xinjiang, China oil-sand The technique that method is effectively washed using thermokalite separates to oil sands bitumen.Therefore, other many new techniques that have been born, such as molten Agent abstraction technique (CN 101274303A, CN 101544902A, CN102925190A, US 3117922 (1964), US 3392105 (1968), US 4046669 (1969), US 4046668 (1977), US 4036732 (1977), US 4347118 (1982), US 4498971 (1984), US 4929341 (1990)), pyrolysis technology (CN103289715A, CN104087329A), microbial fermentation technology etc..These technologies have the advantages of respective, such as, solvent extraction technology has Extraction yield is high, extraction process do not need water participation, can the advantages that operation, solvent can be recycled under normal temperature；Pyrolysis technology Mink cell focus extraction and the integrated processing of oil refining can be realized, reduces technical process；Microbial fermentation technology can be realized gentle Put forward oily process etc..However, they again all along with it is respective the shortcomings that, as the solvent recovery in residual sand solid after solvent extraction is asked Topic and the environmental problem of solvent leakage, the problem of energy consumption is too high in thermal cracking processes, the stability of microbial fermentation and scale Problem, these all cause above-mentioned technology to run into various resistances among course of industrialization, cause it to ultimately fail to industrially real Existing scale uses.
For from mineral composition, it is divided into the mineral intergrowth material based on silicate with the mineral matter of heavy oil field symbiosis, or Mineral matter based on carbonate.Above-mentioned all kinds of researchs are with for the heavy oil field rich in silicate, typical such as Canada oil Sand.And the mink cell focus exploitation for carbonate type (rich in calcium carbonate etc.) is also fewer, mainly due to the heavy of this type Oil typically has stronger active force with mineral matter, and make it that WATER-WASHING METHOD is ineffective.Such mink cell focus is handled using acid wash Ore deposit, effectively mineral component therein can be dissolved, the quality without influenceing mink cell focus, can preferably play and efficiently carry oil Effect.However, the major issue that the technology faces is：There is substantial amounts of waste liquid to produce in production process, contain in waste liquid The materials such as abundant calcium salt, molysite.Therefore, it is also a main technical barrier to solve wastewater problem in recovery process.
As can be seen here, operating cost and environmental problem are current heavy oil field exploitations, especially glossy acid carbonate class oil Sand, key technical problem.Therefore, patent of the present invention will propose that a kind of processing is rich in carbonate mine mainly for above mentioned problem The separation method of the heavy oil field of material.
The content of the invention
It is an object of the invention to provide a kind of low cost, efficient, energy-conservation, it can be used for processing and be rich in carbonate mine material Heavy oil field, such as oil-sand, shale oil, landing oil, greasy filth separation and recovery method rich in carbonate heavy oil field and be System.
The purpose of the present invention is completed using following technical scheme：
A kind of separation and recovery method rich in carbonate heavy oil field, step are as follows
(1) mink cell focus mineral are first passed through below reducing mechanism crushing, then are mixed instead with unitary organic acid or inorganic acid solution Should, obtain containing heavy oil whip, gas, solution, grains of sand residue mixture；
(2) heavy oil whip is diluted after degassing procedure using solvent, and the mixture after dilution is divided into solid-liquid Separation of solid and liquid is carried out from device, obtains solvent heavy oil mixture clear liquid, oil hydrosol and solid precipitation；
(3) gained solvent heavy oil mixture clear liquid enters solvent recovery unit by solvent recovery, while obtains mink cell focus production Product；Oil hydrosol and solid precipitation then enter acid dip pickle and carry out Reaction Separation, and solidliquid mixture, recycling design are obtained after separation Heavy oil mixture；
(4) solidliquid mixture is obtained by filtering after the solution of step (1) and the separation of step (3), solution by adding alkali again Removal of impurities, calcium salt soln is obtained, calcium salt soln recrystallization, obtains calcium salt；
(5) (1) above-mentioned steps obtain grains of sand residue mixture, pickling, precipitation merges to enter using alkali lye caused by filter process Reused after row neutralisation treatment.
Rich in carbonate heavy oil field it is oil-sand, shale oil, landing oil or greasy filth moreover, described, contains carbonic acid in mineral matter Salt is more than 10%.
Moreover, the step (1) middle monoacid acetic acid, nitric acid, hydrochloric acid, hydroiodic acid, hydrobromic acid or formic acid etc., and acid solution PH value is less than 1.
Moreover, the step (1) in mixed reactor be single-stage intermittent operation, or plural serial stage continous way operation Mixing reactor.
Moreover, the step (2) middle equipment for separating liquid from solid include 2~3 grades the solid gravity settling device of liquid and 2~3 grades from Core type separator.
Moreover, the step (2) in the solvent that is added be the Some Petrochemical Byproducts aromatic hydrocarbons such as toluene, gasoline, diesel oil, naphtha The one or more of solvent, addition are 0.5~5 times of heavy oil whip quality.
The step (5) in filter successively, react, filter, crystallizing, or be followed successively by reaction, filtering, the operation of crystallization.
Moreover, (5) middle course of reaction is to add alkali lye to carry out neutralization reaction and precipitation reaction, the alkali added to the step Liquid is the alkaline solutions such as sodium hydroxide solution, potassium hydroxide solution, limewash, stops adding alkali lye when pH value of solution is more than 5.
Moreover, (5) middle crystallization process is evaporation and crystal process to the step, including it is solution concentration, crystallization, separation of solid and liquid, dry It is dry to wait operation.
A kind of separation and recovery method and system rich in carbonate heavy oil field, including：Breaker, hybrid reaction dress Put, foam depassing unit, equipment for separating liquid from solid, solvent recovery unit, pickling reaction unit, filter, neutralization reaction device, Crystallization apparatus, purification residual device and various material transfer equipments and pipe-line equipment, annexation are as follows：
Reducing mechanism material outlet connects mixing reactor, and mixed reactor is also formed with liquid material import, liquids Expect import connection acid solution storage tank, mixed reactor is formed respectively with gas vent, foam outlet, liquid outlet and solid residue Outlet, foam outlet connection foam depassing unit, liquid outlet connection pickling reaction unit, solid residue outlet connection residue are net Makeup is put, and foam depassing unit connection equipment for separating liquid from solid, solvent charge door is formed with connecting pipe, adds solvent, solid-liquid The oil phase outlet connection solvent recovery unit on separator top, solvent enter solvent recovery together with the foam after degassing and filled Put, go oil product to refine after remaining coal tar discharge after solvent recovery unit recycling design, the liquid of equipment for separating liquid from solid bottom Pickling reaction unit is connected with solid outlet, carries out pickling again, the upper oil phase after pickling returns to equipment for separating liquid from solid, lower floor Liquid connect filter entrance with solid outlet, filter solid residue outlet connection purification residual device, filtering dress Liquid outlet connection neutralization precipitation unit is put, neutralization precipitation unit outlet connection crystallization apparatus, neutralization precipitation unit bottom is formed with Precipitation outlet.
The unique distinction following points of the present invention：
1st, the present invention carries out hybrid reaction using acid solution and rich carbonato heavy oil field, and raw material is conveniently easy to get, and grasps Make simply, normal-temperature operation, efficiency high, to reduce cost；
2nd, the present invention is handled emulsion and solid precipitation in mink cell focus froth treatment process using acid wash, can be very Good recycling design and oil, greatly reduce due to environmental problem caused by solvent or the outer row of oil；
3rd, the present invention precipitates to solution caused by mixed reactor and acid dip pickle and solid, using filtering, neutralizes, heavy Form sediment and the mode of crystallization is handled, the effective various useful components reclaimed in mineral so that process harmless discharge, reduce ring Processing cost is protected, improves economic benefit.
Brief description of the drawings
Fig. 1, a kind of separation and recovery method and system flow chart rich in carbonate heavy oil field；
Stock number：1. it is rich in carbonate heavy oil field；2. the heavy oil field after crushing；3. acid solution I；4. gas I (two Carbonoxide)；5. heavy oil whip I；6. calcium salt soln II；7. solid residue (sandy soil)；8. gas II (carbon dioxide)；9. heavy Oil whip II；10. fresh solvent；11. the heavy oil whip after dilution；12. solvent-heavy oil mixture；13. Solids-solution Mixture；14. hydrocarbon class composition；15. recovered solvent；16. acid solution III；17. solvent-mink cell focus foam mixture；18. gas Body III (carbon dioxide)；19. solidliquid mixture；20. filter residue (grains of sand etc. do not allow material, a small amount of)；21. (calcium salt is molten for salting liquid Liquid)；22. alkali lye I；23. alkalinous metal precipitates；24. calcium salt soln；25. water I；26. calcium salt；27. alkali lye II；28. Residual oil；29. Water II；30. residual sand.
Device is numbered：A. reducing mechanism；B. mixed reactor；C. depassing unit；D. equipment for separating liquid from solid；E. solvent returns Receiving apparatus；F. pickling reaction unit；G. filter element；H. neutralization precipitation unit；I. crystallization apparatus；J. purification residual device.
Embodiment
The invention provides a kind of apparatus and method for being used for rich carbonato heavy oil field separation, the separation method makes Reacted with acid solution and heavy oil field, the heavy oil whip of gained is used for solvent dilution and separation of solid and liquid, pickling after reaction Mink cell focus purification process is realized etc. process；And gained waste reaction solution and precipitating residue are then using the side such as filtering, neutralization precipitation, crystallization Method is separately recovered, and finally realizes mink cell focus separation and Extraction and the purpose of accessory substance classification recovery.The separator and method Mink cell focus and various mineral are successfully not only efficiently separated into recovery, accomplish almost zero-emission, and realizes economic, section , it can efficiently run purpose.
Its concrete operation step is as follows：
(1) the heavy oil field rich in carbonate 1 obtains little particle heavy oil field 2 after reducing mechanism A crushing, defeated by material Send machine to deliver in mixing reactor device B, add unitary acid solution 3 and carry out hybrid reaction, dissolve the mineral in heavy oil field Grain, obtain the precipitation such as mink cell focus foam mixture 5, carbon dioxide 4, calcium salt soln 6 and unreacted solid particles of sand 7；
(2) the heavy oil whip 5 obtained removes the carbon dioxide 8 contained in foam into depassing unit C after discharging Go, solvent 10 is added in heavy oil whip 9 after degassing the foam after degasification is diluted；Heavy oil whip after dilution 11 enter equipment for separating liquid from solid D, are divided into upper oil phase clear liquid 12 (solvent and heavy oil mixture), oil hydrosol and solid phase and sink Starch 13；Upper oil phase clear liquid 12 is produced and separated into solvent recovery unit E, and recycling design 15 simultaneously obtains mink cell focus production Product 14, hydrocarbon class composition obtain product oil by operations such as rectifying separation；
(3) oil hydrosol and solid sediment 13 enter pickling reaction unit F progress pickling processes (pickling reaction after discharging Device adds part monoacid extraction raffinate or fresh unitary acid solution 16, gained upper oil phase 17 in mixed reactor (B) and returned Secondary separation is carried out to equipment for separating liquid from solid D；Obtain gas 18 to collect or discharge, caused solution and precipitation are formed after pickling Solidliquid mixture 19, filtered into filter element G, obtain salting liquid 21 and solid filter residue 20 without solid；
(4) above-mentioned solution 21 is input in neutralization precipitation unit H, is added alkali lye 22 and is removed hetero atom alkali metal precipitation 23, Gained calcium salt soln 24 is evaporated crystallization into crystallization apparatus I, obtains product crystals of calcium salts 26, and the water 25 for evaporating gained returns Receive；
(5) the solid filter residue 20 that the sediment 7 in mixed reactor obtains with filter element is separately added into purification residual list First J mixing, adds after appropriate buck 27 washs the safety dumping of residue 30 obtained, and the Residual oil 28 of acquisition reclaims, remaining water Solution 29 discharges.
The acid solution that the present invention uses is unitary organic acid or inorganic acid, such as acetic acid, nitric acid, hydrochloric acid, hydroiodic acid, hydrogen bromine One or more of mixtures of acid, formic acid etc., and acid solution pH value is less than 1.
The solid-to-liquid ratio of the acid solution and heavy oil field is 1：3-10.
Mixed reactor is single-stage intermittent operation in the present invention, or plural serial stage continous way operation mixing reactor.
Equipment for separating liquid from solid includes the solid gravity separator of 2~3 grades of liquid and centrifugal point of 2~3 grades in the present invention From device, such as centrifuge separation or suspension separation.
The solvent for being used for asphalt foam dilution in the present invention is the one of the aromatic hydrocarbon such as toluene, gasoline, diesel oil, naphtha series Kind or several mixtures, use ratio are 0.5~5 times of foam quality.
The alkali lye used is the alkaline solution such as sodium hydroxide solution, potassium hydroxide solution, limewash, concentration 0.01- 10mol/L。
The present invention is realized by following equipment and technical scheme：
A kind of separation and recovery system rich in carbonate heavy oil field, is specifically included：Breaker, mixed reactor, Foam depassing unit, equipment for separating liquid from solid, solvent recovery unit, pickling reaction unit, filter, neutralization reaction device, knot Brilliant device, purification residual device and various material transfer equipments and pipe-line equipment.Annexation is as follows：
Reducing mechanism material outlet connects mixing reactor, and mixed reactor is also formed with liquid material import, liquids Expect import connection acid solution storage tank, mixed reactor is formed respectively with gas vent, foam outlet, liquid outlet and solid residue Outlet, foam outlet connection foam depassing unit, liquid outlet connection pickling reaction unit, solid residue outlet connection residue are net Makeup is put, and foam depassing unit connection equipment for separating liquid from solid, solvent charge door is formed with connecting pipe, adds solvent, solid-liquid The oil phase outlet connection solvent recovery unit on separator top, solvent enter solvent recovery together with the foam after degassing and filled Put, go oil product to refine after remaining coal tar discharge after solvent recovery unit recycling design, the liquid of equipment for separating liquid from solid bottom Pickling reaction unit is connected with solid outlet, carries out pickling again, the upper oil phase after pickling returns to equipment for separating liquid from solid, lower floor Liquid connect filter entrance with solid outlet, filter solid residue outlet connection purification residual device, filtering dress Liquid outlet connection neutralization precipitation unit is put, neutralization precipitation unit outlet connection crystallization apparatus, neutralization precipitation unit bottom is formed with Precipitation outlet.
The concrete operation step of process implementing：
Rich carbonato heavy oil field is crushed within 5cm through reducing mechanism A, and hybrid reaction is delivered to by material conveyor In device device B hybrid reaction is carried out with acid solutions of the pH more than 1.Mink cell focus mineral grain has been dissolved, heavy oil whip has been obtained and mixes Compound, gas, solution and precipitation.The heavy oil whip of acquisition is discharged into the carbon dioxide gas that depassing unit will contain in foam Body removes, and then adds solvent of 0.5~5 times equivalent to foam volume and the foam after degasification is diluted；Bubble after dilution Foam is divided into oil phase clear liquid, oil hydrosol and solid phase precipitation into equipment for separating liquid from solid；Oil phase clear liquid produces and enters solvent and returns Receive unit to be separated, recycling design simultaneously obtains hydrocarbon class composition；Enter descaling bath after oil hydrosol and solid sediment discharge Pickling processes are carried out, gained upper oil phase is back to equipment for separating liquid from solid and separated；After pickling caused solution and precipitation with Solution from mixed reactor is mixed and filtered, and obtains the solution without solid；Alkali lye is added in above-mentioned solution and removes impurity elimination Atom, gained calcium salt soln are evaporated crystallization, obtain product；The solution in sediment and descaling bath in mixed reactor In sediment mixing after with safety dumping after appropriate soda lye wash.
Below, the present invention is illustrated with following examples, but is not limited to following examples.
Embodiment 1：
A kind of separation and recovery method and system rich in carbonate heavy oil field, step are as follows：
(1) oil-sand 15kg (carbonate content 42%, maximum particle diameter 0.5cm) the feedings mixing crushed by reducing mechanism A- The hydrochloric acid for being 1 with pH in reactor B is 1 according to solid-to-liquid ratio：30 (mass ratioes) are sufficiently mixed under normal temperature and reacted 1 hour.
(2) the naphtha of 0.5 times of foam quality of addition after C degasification operation of asphalt foam obtained by above-mentioned reaction is consolidated Liquid separates (two level settles and two-stage centrifugal D), and moisture is less than 3.5% in separating obtained upper oil phase clear liquid, and solid content is small In 1.5%, separated into E, recycling design, while obtain pitch oil product 14, bitumen recovery rate 99.1%.
(3) the emulsion obtained by equipment for separating liquid from solid D and solid precipitation are sent to descaling bath F washings, gained waste liquid and residue precipitation After G is filtered, add sodium hydroxide solution and carry out neutralization precipitation in H, tan precipitate is filtered out, resulting solution enters in I Row crystallization.
(4) the solid residue obtained from mixed reactor B and filter G enters in purification residual device J using neutralization Carry out purified treatment, classification recovery sandy soil and oil residues.
It is final to obtain calcium chloride crystals purity 99.1%, iron hydroxide content 92.5% in tan precipitate, in residue solid Property.
Embodiment 2：
A kind of separation and recovery method and system rich in carbonate heavy oil field, step are as follows：
(1) oil-sand 15kg (carbonate content 61%, maximum particle diameter 5cm) the feedings mixing crushed by reducing mechanism A-anti- Answer in device B with concentration is that the hydrobromic acids of 2 mol/Ls according to solid-to-liquid ratio is 1：3 (mass ratioes) are sufficiently mixed under normal temperature, reaction 120min。
Gained asphalt foam added after C degasification operation 5 times of volumes gasoline carry out separation of solid and liquid (three-level settle with Three-level centrifuges D), moisture is less than 1.5% in separating obtained upper oil phase clear liquid, and solid content is less than 1.5%, enters into E Row separation, recycling design, while pitch oil product 14 is obtained, bitumen recovery rate 98.7%.
(3) the emulsion obtained by equipment for separating liquid from solid D and solid precipitation are sent to descaling bath F washings, gained waste liquid and residue precipitation After G is filtered, filtrate enters in neutralization precipitation device H, adds limewash and carries out neutralization precipitation, tan precipitate is filtered out, institute Solution enters to be advanced into I and is evaporated crystallization.
(4) the solid residue obtained from mixed reactor B and filter G enters in purification residual device J using neutralization Carry out purified treatment, classification recovery sandy soil and oil residues.
It is final to obtain calcium chloride crystals purity 99.8%, iron hydroxide content 94.3% in tan precipitate, in residue solid Property.
Embodiment 3：
A kind of separation and recovery method and system rich in carbonate heavy oil field, step are as follows：
(1) greasy filth 15kg (carbonate content 56%, maximum particle diameter 1.5cm) the feedings mixing crushed by reducing mechanism A- The nitric acid in reactor B with concentration being 3 mol/Ls according to solid-liquid ratio is 1：3 (mass ratioes) are sufficiently mixed under normal temperature, reaction 120min。
Gained asphalt foam added after C degasification operation 5 times of volumes naphtha and kerosene (volume ratio, 1:1) enter Row separation of solid and liquid (two-stage settle with three-level suspension D), moisture is less than 1.5% in separating obtained upper oil phase clear liquid, admittedly contain Amount is less than 1.5%, is separated into E, recycling design, while obtains pitch oil product 14, bitumen recovery rate 99.3%.
(3) the emulsion obtained by equipment for separating liquid from solid D and solid precipitation are sent to descaling bath F washings, gained waste liquid and residue precipitation After G is filtered, filtrate enters in neutralization precipitation device H, adds limewash and carries out neutralization precipitation, tan precipitate is filtered out, institute Solution enters to be advanced into I and is evaporated crystallization.
(4) the solid residue obtained from mixed reactor B and filter G enters in purification residual device J using neutralization Carry out purified treatment, classification recovery sandy soil and oil residues.
It is final to obtain calcium nitrate crystal purity 97.8%, iron hydroxide content 93.7% in tan precipitate, in residue solid Property.
Embodiment 4：
A kind of separation and recovery method and system rich in carbonate heavy oil field, step are as follows：
(1) oil shale 15kg (carbonate content 52%, maximum particle diameter 5cm) the feedings mixing crushed by reducing mechanism A- The acetic acid in reactor B with concentration being 5 mol/Ls according to solid-liquid ratio is 1：3 (mass ratioes) mix at 65 DEG C, reaction 30min, mixed reactor B are two-stage series connection, i.e., one-level is hybrid reaction, and another level is flotation.
Gained asphalt foam added after C degasification operation 5 times of volumes toluene carry out separation of solid and liquid (two-stage settle with Two-stage suspension separates D), moisture is less than 1.2% in separating obtained upper oil phase clear liquid, and solid content is less than 1.5%, into E In separated, recycling design, while obtain pitch oil product 14, bitumen recovery rate 99.7%.
(3) the emulsion obtained by equipment for separating liquid from solid D and solid precipitation are sent to descaling bath F washings, gained waste liquid and residue precipitation After G is filtered, filtrate enters in neutralization precipitation device H, adds limewash and carries out neutralization precipitation, tan precipitate is filtered out, institute Solution enters to be advanced into I and is evaporated crystallization.
(4) the solid residue obtained from mixed reactor B and filter G enters in purification residual device J using neutralization Carry out purified treatment, classification recovery sandy soil and oil residues.
Final to obtain calcium acetate purity 97.5%, iron hydroxide content 93.4% in tan precipitate, residue solid is neutral.
Embodiment 5：
A kind of separation and recovery method and system rich in carbonate heavy oil field, step are as follows：
(1) oil-sand 15kg (carbonate content 52%, maximum particle diameter 3cm) the feedings mixing crushed by reducing mechanism A-anti- Answer in device B with concentration is that the formic acid of 1 mol/L according to solid-liquid ratio is 1：6 (mass ratioes) are sufficiently mixed at 25 DEG C, reaction 30min, mixed reactor B are two-stage series connection, i.e., two-stage mixing reactor alternately reacts operates with stratification.
Gained asphalt foam added after C degasification operation 5 times of volumes kerosene carry out separation of solid and liquid (two-stage settle with Two-stage suspension separates D), moisture is less than 2.5% in separating obtained upper oil phase clear liquid, and solid content is less than 1.5%, into E In separated, recycling design, while obtain pitch oil product 14, bitumen recovery rate 99.6%.
(3) the emulsion obtained by equipment for separating liquid from solid D and solid precipitation are sent to descaling bath F washings, gained waste liquid and residue precipitation After G is filtered, filtrate enters in neutralization precipitation device H, adds limewash and carries out neutralization precipitation, tan precipitate is filtered out, institute Solution enters to be advanced into I and is evaporated crystallization.
(4) the solid residue obtained from mixed reactor B and filter G enters in purification residual device J using neutralization Carry out purified treatment, classification recovery sandy soil and oil residues.
Final to obtain calcium formate purity 98.9%, coal tar solid content is less than 1%, and residue solid is neutral.
A kind of apparatus and method rich in the separation of carbonate heavy oil field proposed by the present invention, have passed through preferred embodiment Be described, person skilled substantially can not depart from present invention, in spirit and scope to structure as described herein It is modified or is suitably changed with combining with technical method, realizes the technology of the present invention.In particular, it is all similar As replace and change it is apparent to those skilled in the art, they be considered as being included in spirit of the invention, In scope and content.

Claims (7)

  1. A kind of 1. separation and recovery method rich in carbonate heavy oil field, it is characterised in that：Step is as follows
    Mink cell focus mineral first pass through reducing mechanism crush it is following, then with unitary organic acid or inorganic acid solution hybrid reaction, obtain To containing heavy oil whip, gas, solution, grains of sand residue mixture；
    (2) heavy oil whip is diluted after degassing procedure using solvent, and the mixture after dilution is filled into separation of solid and liquid Carry out separation of solid and liquid is put, obtains solvent heavy oil mixture clear liquid, oil hydrosol and solid precipitation；
    (3) gained solvent heavy oil mixture clear liquid enters solvent recovery unit by solvent recovery, while obtains hydrocarbon class composition； Oil hydrosol and solid precipitation then enter acid dip pickle and carry out Reaction Separation, and solidliquid mixture, recycling design weight are obtained after separation Matter oil mixture；
    (4) the solution of step (1) is with obtaining solidliquid mixture by filtering after the separation of step (3), and solution passes through again plus alkali removes It is miscellaneous, calcium salt soln is obtained, calcium salt soln recrystallization, obtains calcium salt；
    (5) (1) above-mentioned steps obtain grains of sand residue mixture, pickling, the caused precipitation merging of filter process using in alkali lye progress Reused with after processing；
    Be rich in carbonate heavy oil field is oil-sand, shale oil, landing oil or greasy filth, and the content of carbonate exceedes in mineral 10%；
    The step (1) middle monoacid acetic acid, nitric acid, hydrochloric acid, hydroiodic acid, hydrobromic acid or formic acid, and acid solution pH value is less than 1；
    The step (2) in the solvent that is added be toluene, gasoline, diesel oil, the one or more of naphtha, addition is heavy 0.5~5 times of oil whip quality.
  2. 2. the separation and recovery method according to claim 1 rich in carbonate heavy oil field, it is characterised in that：The step (1) the mixed reactor in is single-stage intermittent operation, or plural serial stage continous way operation mixing reactor.
  3. 3. the separation and recovery method according to claim 1 rich in carbonate heavy oil field, it is characterised in that：The step (2) middle equipment for separating liquid from solid includes 2~3 grades of the solid gravity settling device of liquid and 2~3 grades of centrifugal separator.
  4. 4. the separation and recovery method according to claim 1 rich in carbonate heavy oil field, it is characterised in that：The step (3) for step, (1) a part for pickle or fresh pickle, upper oil phase obtained by after pickling are recycled to solid-liquid to the pickle in Separator；The step (4) in filter successively, react, filter, crystallizing, or be followed successively by reaction, filtering, the behaviour of crystallization Make.
  5. 5. the separation and recovery method according to claim 1 rich in carbonate heavy oil field, it is characterised in that：The step (4) middle course of reaction is to add alkali lye to carry out neutralization reaction and precipitation reaction, and the alkali lye added is sodium hydroxide solution, hydrogen-oxygen Change potassium solution, limewash, stop adding alkali lye when pH value of solution is more than 5.
  6. 6. the separation and recovery method according to claim 1 rich in carbonate heavy oil field, it is characterised in that：The step (4) middle crystallization process is evaporation and crystal process, including solution concentration, crystallization, separation of solid and liquid, drying process.
  7. A kind of 7. separation and recovery system rich in carbonate heavy oil field, it is characterised in that including：Breaker, hybrid reaction Device, foam depassing unit, equipment for separating liquid from solid, solvent recovery unit, pickling reaction unit, filter, neutralization reaction dress Put, crystallization apparatus, purification residual device and various material transfer equipments and pipe-line equipment, annexation it is as follows：
    Reducing mechanism material outlet connects mixing reactor, and mixed reactor is also formed with liquid material import, and liquid material enters Mouth connection acid solution storage tank, mixed reactor are formed respectively with gas vent, foam outlet, liquid outlet and solid residue and gone out Mouthful, foam outlet connection foam depassing unit, liquid outlet connection pickling reaction unit, solid residue outlet connection purification residual Device, foam depassing unit connection equipment for separating liquid from solid, is formed with solvent charge door on connecting pipe, adds solvent, solid-liquid point From the oil phase outlet connection solvent recovery unit on device top, solvent enters solvent recovery unit together with the foam after degassing, Oil product is gone to refine after the discharge of remaining coal tar after solvent recovery unit recycling design, the liquid of equipment for separating liquid from solid bottom and solid Body outlet connection pickling reaction unit, carries out pickling again, the upper oil phase after pickling returns to equipment for separating liquid from solid, the liquid of lower floor Body connects filter entrance, filter solid residue outlet connection purification residual device, filter liquid with solid outlet Body outlet connection neutralization precipitation unit, neutralization precipitation unit outlet connection crystallization apparatus, neutralization precipitation unit bottom is formed with precipitation Outlet.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1055552A (en) * 1990-04-04 1991-10-23 切夫里昂研究公司 Remove metal in the hydrocarbon feed with the salt of sulfuric acid and it
CN1066284A (en) * 1991-04-30 1992-11-18 张文进 The oil shale mine material remove conversion process
US5277796A (en) * 1991-10-03 1994-01-11 Institute Of Gas Technology Pretreating oil shale with organic acid to increase retorting yield and process efficiency
CN1408017A (en) * 1999-11-16 2003-04-02 Rmg服务控股有限公司 Treatment of crude oils
CN1431276A (en) * 2002-01-10 2003-07-23 中国石油化工股份有限公司 Method for removing metal from hydrocarbon oil by using inorganic acid
CN1431277A (en) * 2002-01-10 2003-07-23 中国石油化工股份有限公司 Demetallization agent for hy drocarbon oil and its operation method
CN103896466A (en) * 2012-12-26 2014-07-02 郭公甫 Dirty oil sludge decomposition method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1055552A (en) * 1990-04-04 1991-10-23 切夫里昂研究公司 Remove metal in the hydrocarbon feed with the salt of sulfuric acid and it
CN1066284A (en) * 1991-04-30 1992-11-18 张文进 The oil shale mine material remove conversion process
US5277796A (en) * 1991-10-03 1994-01-11 Institute Of Gas Technology Pretreating oil shale with organic acid to increase retorting yield and process efficiency
CN1408017A (en) * 1999-11-16 2003-04-02 Rmg服务控股有限公司 Treatment of crude oils
CN1431276A (en) * 2002-01-10 2003-07-23 中国石油化工股份有限公司 Method for removing metal from hydrocarbon oil by using inorganic acid
CN1431277A (en) * 2002-01-10 2003-07-23 中国石油化工股份有限公司 Demetallization agent for hy drocarbon oil and its operation method
CN103896466A (en) * 2012-12-26 2014-07-02 郭公甫 Dirty oil sludge decomposition method

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