CN106010620B - Separation recovery method and system for the heavy oil resources for handling carbonate containing mineral matter - Google Patents
Separation recovery method and system for the heavy oil resources for handling carbonate containing mineral matter Download PDFInfo
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- CN106010620B CN106010620B CN201610298739.4A CN201610298739A CN106010620B CN 106010620 B CN106010620 B CN 106010620B CN 201610298739 A CN201610298739 A CN 201610298739A CN 106010620 B CN106010620 B CN 106010620B
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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
Abstract
The present invention is a kind of separation recovery method for the heavy oil resources for being used to handle carbonate containing mineral matter.It is characterized in that：The heavy oil resources of carbonate containing mineral matter, such as oil-sand, oil shale, ground sludge, mix with the solution and chemical addition agent configured, react in any case, mineral matter in heavy oil field is dissolved, so as to reach mink cell focus target separated 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, but also greatly saves the energy, realizes energy saving, the emission reduction production purpose of room temperature extraction or recycling mink cell focus.
Description
Technical field
The present invention relates to it is a kind of be used for handle carbonate containing mineral matter heavy oil resources separation recovery method and system,
Belong to chemical separating and reaction engineering technical field, and in particular to the methods of crushing, react, settling, filtering, distilling, crystallizing.
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 injection 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 oil sands bitumen.For this reason, other many new techniques that have been born, such as molten
Agent abstraction technique (CN 101274303A, CN 101544902A, CN102925190 A, 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 be not required water participation, can the advantages that operation, solvent can be recycled under room temperature；Pyrolysis technology
It can realize mink cell focus extraction and the integrated processing of oil refining, reduce technical process；Microbial fermentation technology can be realized gentle
Put forward oily process etc..However, they again all with it is respective the shortcomings that, as the solvent recovery in residual sand solid after solvent extraction is asked
The problem of topic and environmental problem of solvent leakage, energy consumption is excessive 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 generally 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 can dissolve mineral component therein, and the quality without influencing 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 wastewater problem to be solved in recovery process.
It can be seen from the above that operating cost and environmental problem are current heavy oil field exploitations, especially glossy acid carbonate class oil
Sand, key technical problem.For this reason, patent of the present invention will propose that a kind of processing is rich in carbonate mine mainly for the above 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 inexpensive, efficient, energy saving, it can be used for processing and be rich in carbonate mine material
Mink cell focus ore resources, such as oil-sand, shale oil, landing oil, greasy filth separation recovery method and system.
The present invention is realized by following equipment and technical solution：
A kind of the separation recovery method and system of the heavy oil resources for being used to handle carbonate containing mineral matter, its feature exist
In operating procedure is as follows：
Mink cell focus mineral first pass through reducing mechanism crushing, then with unitary acid solution hybrid reaction, obtain containing mink cell focus
Foam, gas, calcium salt soln, 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；And oil hydrosol and solid precipitation then enter acid dip pickle and carry out Reaction Separation；
(4) acid dip pickle produces gas, solvent naphtha, solution, asphalitine and sandy soil, gained solvent naphtha and is back to separation of solid and liquid
Device, asphalitine are individually extracted by enrichment；
(5) step salting liquid and sandy soil residue that (4) pickling produces recycles salt production therein after filtering, react, crystallize
Product；
(6) residue mixture that (1) step produces and step (5) filter generation sandy soil residue discharged after alkali neutralization or
Person recycles.
Moreover, handled heavy oil field is the heavy oil field rich in carbonate mine material, such as oil-sand, shale oil, landing
Oil, greasy filth.
Moreover, the step (1) in the acid solution of heavy oil field hybrid reaction be hydrobromic acid, formic acid, and acid solution pH value
Less than 1.
Moreover, the step (1) in hybrid reaction system be single-stage intermittent operation, or plural parallel stage alternating is continuous
Formula operates, or plural serial stage continous way operation mixing reactor.
Moreover, (2) middle equipment for separating liquid from solid includes 1~3 grade of liquid and consolidates gravity settling device and 1~3 grade the step
Centrifugal separator.
Moreover, the step (2) in the solvent that is added be chain hydrocarbon solvent one or more of mixtures, addition
For 0.5~5 times of heavy oil whip quality.
Moreover, the chain hydrocarbon solvent is pentane, hexane, heptane.
Moreover, (5) middle reaction process is to add lye to carry out neutralization reaction and precipitation reaction to the step, added
Lye is the alkaline solutions such as sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide, limewash, stops lye when pH value of solution is more than 5
Addition.
Moreover, (5) middle crystallization process is dilution crystallization process to the step, used dissolved agent is methanol, ethanol,
Ether, acetone and other organic solvent, its addition are 0.3~5 times of salting liquid volume.
A kind of the separation recovery method and system of the heavy oil resources for being used to handle carbonate containing mineral matter, composition are as follows：
Breaker material outlet connects mixed reactor, and mixed reactor is also formed with liquid material import, liquid
Material inlet connects acid solution storage tank, and it is residual that mixed reactor is formed respectively with gas vent, foam outlet, liquid outlet and solid
Slag exports, foam outlet connection foam depassing unit, liquid outlet connection pickling reaction unit, solid residue outlet connection residue
Purifier, foam depassing unit connection equipment for separating liquid from solid, solvent charge door is formed with connecting pipe, adds solvent, Gu
The oil phase outlet connection solvent recovery unit on liquid separating apparatus top, solvent enter separation of solid and liquid together with the foam after degassing and fill
Put, the top oil phase outlet connection solvent recovery unit of equipment for separating liquid from solid, remaining drip after solvent recovery unit recycling design
Oil product is gone to refine after blue or green oil discharge；The liquid of equipment for separating liquid from solid lower part connects pickling reaction unit with solid outlet, carries out again
Secondary pickling, the upper oil phase after pickling return to equipment for separating liquid from solid, and gas vent is connected to gas recycling and processing device, lower floor
Liquid connects filtration apparatus entrance with sandy soil solid outlet, and the asphalitine solid of generation is discharged through asphalitine outlet, filtering dress
Put solid residue outlet connection purification residual device, filtration apparatus liquid outlet connection neutralization precipitation unit, neutralization precipitation unit
Lower part is formed with precipitation outlet, and neutralization precipitation unit liquid outlet connection crystalline substance device, crystallization apparatus is formed with dissolved agent import, is passed through
Dissolved agent.
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, acid solution can by oil from
Grains of sand surface extractions come out, and oil and sand are totally separated from out, and realize the complete recycling and the harmless processing of the grains of sand of oil, raw material side
Easy, it is easy to operate, it is efficient, reduce cost.
2nd, in mink cell focus froth treatment process of the present invention, lotion and solid precipitation are handled using acid wash, not only can be with
Good recycling design and oil, moreover it is possible to the heavy constituent in selective extraction mink cell focus, such as asphalitine, reduce due to solvent or
Environmental problem caused by oily outer row, at the same can also effectively prevent the fouling that occurs in the following process of hydrocarbon class composition or
Block, poison the problems such as catalyst.
3rd, the solution and solid that the present invention produces hybrid reaction system and pickling system precipitate, and using filtering, neutralize, heavy
Form sediment and the mode of crystallization is handled, the effective various useful components recycled in mineral so that process harmless discharge, reduces ring
Protect processing cost；And effectively reduced the energy consumption by the way of dilution crystallization, improve whole economic efficiency.
Brief description of the drawings
Fig. 1 are used for the separation recovery method and system flow chart for handling the heavy oil resources of carbonate containing mineral matter
Stock number：1. it is rich in carbonate heavy oil field；2. the heavy oil field after crushing；3. acid solution I (monoacid)；4.
Gas I (carbon dioxide)；5. heavy oil whip I；6. acid solution II (reaction extraction raffinate)；7. solid residue (sandy soil)；8. gas II
(carbon dioxide)；9. heavy oil whip II；10. solvent (chain hydrocarbon)；11. the heavy oil whip after dilution；12. solvent-mink cell focus
Mixture；13. Solids-solution mixture；14. hydrocarbon class composition；15. recovered solvent；16. asphalitine；17. fresh acid is molten
Liquid；18. gas III (carbon dioxide)；19. solidliquid mixture；20. solvent-mink cell focus foam mixture；21. salting liquid；22. filter
Slag；23. lye I；24. calcium salt soln；25. metal alkali compound precipitates；26. dissolved agent；27. water I；28. calcium salt；29. lye II；
30. residual sand；31. water II.
Device is numbered：A. pulverizer；B. mixing reactor；C. depassing unit；D. equipment for separating liquid from solid；E. solvent recovery fills
Put；F. pickling reaction unit；G. filter element；H. neutralization precipitation unit；I. crystallization apparatus；J. purification residual device.
Embodiment
, should the present invention provides the separation recovery method and system of the heavy oil resources for handling carbonate containing mineral matter
Separation method is reacted using acid solution and heavy oil field, and the heavy oil whip of gained is using solvent dilution and solid-liquid after reaction
The processes such as separation, pickling realize mink cell focus purification process；And gained waste reaction solution and precipitating residue then use filtering, neutralize, is heavy
The methods of forming sediment, crystallizing is separately recovered, and finally realizes mink cell focus separation and Extraction and the purpose of accessory substance classification recycling.To heavy
Oil whip is handled using chain hydrocarbon, can not only reduce the moisture and mineral content in mink cell focus, can also be by asphalitine etc.
Heavy constituent precipitates, and improves the quality of hydrocarbon class composition.It is heavy using filtering and chemistry during to liquid and waste slag produced processing
Form sediment, the method for dilution crystallization, not only all kinds of mineral compositions are separately recovered, but also can also be significantly energy saving.The separation
Mink cell focus and various mineral are not only successfully efficiently separated recycling by system and method, but also are realized economical, energy saving, high
The operation purpose of effect.
Heavy oil separating method of the present invention rich in carbonate mine material includes following main device：Pulverizer,
Mixing reactor, depassing unit, sedimentation device, equipment for separating liquid from solid, distilling apparatus, filtration apparatus, crystallization apparatus and material are defeated
Send equipment etc..
Its concrete operation step is as follows：
(1) the heavy oil field 2 after rich carbonato heavy oil field 1 is crushed after pulverizer A crushing, it is defeated by material
Send machine to send into mixing reactor device B and carry out hybrid reaction with unitary acid solution 3, dissolve mineral grain therein, weighed
Matter oil whip mixture 5, gas 4, solution 6 (calcium salt soln) and precipitation 7 (the mainly grains of sand)；
(2) the mink cell focus foam mixture 5 obtained is discharged into the carbon dioxide 8 that depassing unit C will contain in foam
Remove, then add solvent 10 and the heavy oil whip 9 after degassing is diluted；Heavy oil whip 11 after dilution enters solid-liquid
D points of separator is oil phase clear liquid 12, oil hydrosol and solid phase precipitate 13；Oil phase clear liquid produces and enters solvent recovery unit
E is separated, and recycling design 15 simultaneously obtains hydrocarbon class composition 14；
(3) oil hydrosol and solid sediment 13 enter pickling reaction unit F progress pickling processes after discharging, used
Acid returns for the part extraction raffinate 6 in mixed reactor B and the mixture of fresh acid solution 17, gained upper oil phase, part oil phase 20
It is back to equipment for separating liquid from solid D to be separated, another part heavy constituent solid 16, such as asphalitine, then independent extraction processing, the component
Larger to the viscosity influence of coal tar, it is separated from coal tar can improve 14 quality of product of coal tar, prevent viscous greatly
The pitch of degree influences rectification efficiency, influences the situation inside device；
The gas 18 of pickling reaction unit is discharged；Solution and the sandy soil precipitation 19 produced after pickling is expelled to filter element G
Filtering, obtains salting liquid 21 and filter residue 22 without solid；
(4) above-mentioned salting liquid 21 is input in neutralization precipitation unit H, adds lye 23, removes metal alkali compound precipitation 25
(metal ion, such as iron, manganese, nickel, copper, magnesium), gained calcium salt soln 24 are input to crystallization apparatus I after concentration, add molten
Analyse agent 26 and carry out dilution crystallization, obtain calcium salt product 28, evaporate the recycling of water 27；
(5) the sediment 7 in mixed reactor is added to purification residual device J after being mixed with filter residue 22, with appropriate alkali
Water 29 obtains residual sand 30 and water 31, safety dumping after washing.Sand is reusable or utilizes.
The acid solution that the present invention uses is unitary organic acid or inorganic acid, such as hydrobromic acid, formic acid, and acid solution pH value is small
In 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 parallel stage alternating continous way operation, or multistage
Continous way of connecting operation mixing reactor.
Equipment for separating liquid from solid includes that 1~3 grade of liquid consolidates gravity separator and 1~3 grade in the present invention centrifugal point
From device, such as centrifuge separation or suspension separation.
Liquid and waste slag produced processing in the present invention can be successively filter, react, filtering, crystallization, or be followed successively by reaction,
Filtering, the operation of crystallization.
Crystallization process in the present invention is dilution crystallization process, and used dissolved agent is methanol, ethanol, ether, acetone
Deng organic solvent, its addition is 0.3~5 times of salting liquid volume.
The core apparatus of the separation and Extraction process rich in carbonate heavy oil field, includes five big main devices in the present invention：
Mineral acid solution mixing-reaction unit, mink cell focus foam treatment device, foam pickling retracting device, mineral qualitative classification retracting device
And solvent recovery cycle device.
Specifically include breaker, mixed reactor, depassing unit, equipment for separating liquid from solid, solvent recovery unit, pickling
Reaction unit, filtration apparatus, neutralization reaction device, crystallization apparatus, purification residual device and various material transfer equipments and pipeline
Equipment, concrete structure are as follows：
Breaker material outlet connects mixed reactor, and mixed reactor is also formed with liquid material import, liquid
Material inlet connects acid solution storage tank, and it is residual that mixed reactor is formed respectively with gas vent, foam outlet, liquid outlet and solid
Slag exports, foam outlet connection foam depassing unit, liquid outlet connection pickling reaction unit, solid residue outlet connection residue
Purifier, foam depassing unit connection equipment for separating liquid from solid, solvent charge door is formed with connecting pipe, adds solvent, Gu
The oil phase outlet connection solvent recovery unit on liquid separating apparatus top, solvent enter separation of solid and liquid together with the foam after degassing and fill
Put, the top oil phase outlet connection solvent recovery unit of equipment for separating liquid from solid, remaining drip after solvent recovery unit recycling design
Oil product is gone to refine after blue or green oil discharge；The liquid of equipment for separating liquid from solid lower part connects pickling reaction unit with solid outlet, carries out again
Secondary pickling, the upper oil phase after pickling return to equipment for separating liquid from solid, and gas vent is connected to gas recycling and processing device, lower floor
Liquid connects filtration apparatus entrance with sandy soil solid outlet, and the asphalitine solid of generation is discharged through asphalitine outlet, filtering dress
Put solid residue outlet connection purification residual device, filtration apparatus liquid outlet connection neutralization precipitation unit, neutralization precipitation unit
Lower part is formed with precipitation outlet, and neutralization precipitation unit liquid outlet connection crystalline substance device, crystallization apparatus is formed with dissolved agent import, is passed through
Dissolved agent.
The concrete operation step of process implementing：
(1) rich carbonato heavy oil field is crushed within 5cm through pulverizer A, is sent by material conveyor to hybrid reaction
The acid solution for being more than 0.1 mol/L in device device B with concentration carries out hybrid reaction.
(2) mink cell focus mineral grain has been dissolved, has obtained mink cell focus foam mixture, gas, solution and precipitation.
(3) the heavy oil whip obtained is discharged into depassing unit C and removes the carbon dioxide contained in foam, so
Solvent of 0.5~5 times equivalent to foam quality is added afterwards to be diluted the foam after degasification.
(4) it is oil phase clear liquid, oil hydrosol and solid phase precipitation that the foam after diluting, which enters D points of equipment for separating liquid from solid,；Oil phase
Clear liquid produces and enters solvent recovery unit and separated, and recycling design simultaneously obtains hydrocarbon class composition；Oil hydrosol and solid sink
Enter pickling reaction unit F after starch discharge and carry out pickling processes, gained upper oil phase is back to equipment for separating liquid from solid D and is divided
From another part coal tar solid (asphalitine) is then produced as one of byproduct.
(5) the solution and precipitation produced after pickling is filtered, and obtains the solution without solid；Alkali is added in above-mentioned solution
Liquid removes hetero atom, and gained calcium salt soln is concentrated.Solution after concentration adds dissolved agent and is crystallized, and obtains product.
(6) with appropriate buck after the sediment in mixed reactor is mixed with the sediment in the solution in descaling bath
Safety dumping after washing.
In the following, being illustrated to the present invention with following embodiments, but it is not limited to following embodiments.
Embodiment 1：
Separation recovery method and system, operating procedure for the heavy oil resources that handle carbonate containing mineral matter is as follows：
(1) oil-sand 15kg (carbonate content 42%, maximum particle diameter 0.5cm) the feedings mixing crushed by pulverizer A-anti-
It according to solid-to-liquid ratio is 1 to answer the hydrobromic acid for being 1 with pH in device B：30 (mass ratioes) be sufficiently mixed under room temperature and react 1 it is small when.
(2) gained asphalt foam adds heptane progress separation of solid and liquid (the level-one sedimentation of 0.5 times of quality after C degasification operation
With first-stage centrifugal D), moisture is less than 3.5% in separating obtained upper oil phase clear liquid, and solid content is less than 1.5%, into E
Separated, recycling design, while obtain pitch oil product 14, pitch oil recovery rate 79.3%, coal tar studies on asphaltene content
Less than 10%.
(3) the lotion obtained by equipment for separating liquid from solid D and solid precipitation are sent to pickling reaction unit F washings, upper oil phase circulation
To equipment for separating liquid from solid D, the then individually extraction discharge of solid bituminite 16.
(4) it is anti-in neutralizing to add sodium hydroxide after G is filtered for waste liquid obtained by pickling reaction unit F and residue sandy soil precipitation
Answer and neutralization precipitation is carried out in device H, tan precipitate is filtered out, the ether that 0.3 times of volume is added after resulting solution is concentrated carries out
Dilution crystallization.
(5) the sediment in the sediment in mixed reactor B and the solution in pickling reaction unit F is in purification residual
With safety dumping after appropriate soda lye wash after being mixed in device J.
It is final to obtain calcium bromide crystal purity 99.3%, iron hydroxide content 93.5% in tan precipitate, in residue solid
Property.
Embodiment 2：
Separation recovery method and system, operating procedure for the heavy oil resources that handle carbonate containing mineral matter is as follows：
(1) the oil-sand 15kg (carbonate content 61%, maximum particle diameter 5cm) crushed by pulverizer A is sent into mixing-reaction
The hydrobromic acid in device B with concentration being 2 mol/Ls according to solid-to-liquid ratio is 1：3 (mass ratioes) are sufficiently mixed under room temperature, reaction
120min。
Gained asphalt foam added after C degasification operation 5 times of quality heptane carry out separation of solid and liquid (level-one 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%, into E into
Row separates, recycling design, while obtains pitch oil product 14, pitch oil recovery rate 85.2%, and coal tar studies on asphaltene content is small
In 5%.
(3) the lotion obtained by equipment for separating liquid from solid D and solid precipitation are sent to pickling reaction unit F washings, upper oil phase circulation
To equipment for separating liquid from solid D, the then individually extraction discharge of solid bituminite 16.
(4) it is anti-in neutralizing to add sodium hydroxide after G is filtered for waste liquid obtained by pickling reaction unit F and residue sandy soil precipitation
Answer and neutralization precipitation is carried out in device H, tan precipitate is filtered out, the ether progress that 2 times of volumes are added after resulting solution is concentrated is molten
Analysis crystallization.
(5) the sediment in the sediment in mixed reactor B and the solution in pickling reaction unit F is in purification residual
With safety dumping after appropriate soda lye wash after being mixed in device J.
It is final to obtain calcium bromide crystal purity 99.4%, iron hydroxide content 94.2% in tan precipitate, in residue solid
Property.
Embodiment 3：
Separation recovery method and system, operating procedure for the heavy oil resources that handle carbonate containing mineral matter is as follows：
(1) greasy filth 15kg (carbonate content 56%, maximum particle diameter 1.5cm) the feedings mixing crushed by pulverizer A-anti-
Answer in device B with concentration is that the formic acid of 3 mol/Ls according to solid-liquid ratio is 1：3 (mass ratioes) are sufficiently mixed under room temperature, reaction
120min。
Gained asphalt foam added after C degasification operation 3 times of quality pentane carry out 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, and solid content is less than 1.5%, into E into
Row separates, recycling design, while obtains pitch oil product 14, pitch oil recovery rate 82.5%, and coal tar studies on asphaltene content is small
In 3.5%.
(3) the lotion obtained by equipment for separating liquid from solid D and solid precipitation are sent to pickling reaction unit F washings, upper oil phase circulation
To equipment for separating liquid from solid D, the then individually extraction discharge of solid bituminite 16.
(4) it is anti-in neutralizing to add sodium hydroxide after G is filtered for waste liquid obtained by pickling reaction unit F and residue sandy soil precipitation
Answer and neutralization precipitation is carried out in device H, tan precipitate is filtered out, the ethanol progress that 5 times of volumes are added after resulting solution is concentrated is molten
Analysis crystallization.
(5) the sediment in the sediment in mixed reactor B and the solution in pickling reaction unit F is in purification residual
With safety dumping after appropriate soda lye wash after being mixed in device J.
It is final to obtain calcium formate crystal purity 97.3%, iron hydroxide content 93.5% in tan precipitate, in residue solid
Property.
Embodiment 4：
Separation recovery method and system, operating procedure for the heavy oil resources that handle carbonate containing mineral matter is as follows：
(1) oil shale 15kg (carbonate content 52%, maximum particle diameter 5cm) the feedings mixing crushed by pulverizer A-anti-
Answer in device B with concentration is that the formic acid of 5 mol/Ls according to solid-liquid ratio is 1：3 (mass ratioes) mix at 65 DEG C, react 30min,
Mixed reactor B is two-stage series connection, i.e., level-one is hybrid reaction, and another level is flotation.
Gained asphalt foam added after C degasification operation 5 times of quality hexane 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, pitch oil recovery rate 85.7%, coal tar studies on asphaltene contains
Amount is less than 3%.
(3) the lotion obtained by equipment for separating liquid from solid D and solid precipitation are sent to pickling reaction unit F washings, upper oil phase circulation
To equipment for separating liquid from solid D, the then individually extraction discharge of solid bituminite 16.
(4) it is anti-in neutralizing to add sodium hydroxide after G is filtered for waste liquid obtained by pickling reaction unit F and residue sandy soil precipitation
Answer and neutralization precipitation is carried out in device H, tan precipitate is filtered out, the acetone progress that 5 times of volumes are added after resulting solution is concentrated is molten
Analysis crystallization.
(5) the sediment in the sediment in mixed reactor B and the solution in pickling reaction unit F is in purification residual
With safety dumping after appropriate soda lye wash after being mixed in device J.
Final to obtain calcium formate purity 97.5%, iron hydroxide content 93.2% in tan precipitate, residue solid is neutral.
Embodiment 5：
Separation recovery method and system, operating procedure for the heavy oil resources that handle carbonate containing mineral matter is as follows：
(1) the oil-sand 15kg (carbonate content 52%, maximum particle diameter 3cm) crushed by pulverizer A is sent into mixing-reaction
The formic acid in device B with concentration being 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 parallel connection, i.e., two-stage mixing reactor is alternately reacted operates with stratification.
(2) gained asphalt foam adds the hexane and heptane mixture (volume ratio 1 of 5 times of quality after C degasification operation:
1) separation of solid and liquid (two-stage sedimentation separates D with two-stage suspension) is carried out, moisture is less than in separating obtained upper oil phase clear liquid
2.5%, solid content is less than 1.5%, is separated into E, recycling design, while obtains pitch oil product 14, and coal tar returns
Yield 87.2%, asphaltenes are less than 6.5% in coal tar.
(3) the lotion obtained by equipment for separating liquid from solid D and solid precipitation are sent to pickling reaction unit F washings, upper oil phase circulation
To equipment for separating liquid from solid D, the then individually extraction discharge of solid bituminite 16.
(4) it is anti-in neutralizing to add sodium hydroxide after G is filtered for waste liquid obtained by pickling reaction unit F and residue sandy soil precipitation
Answer and neutralization precipitation is carried out in device H, tan precipitate is filtered out, the acetone progress that 5 times of volumes are added after resulting solution is concentrated is molten
Analysis crystallization.
(5) the sediment in the sediment in mixed reactor B and the solution in pickling reaction unit F is in purification residual
With safety dumping after appropriate soda lye wash after being mixed in device J.
Final to obtain calcium formate purity 98.9%, residue solid is neutral.
Embodiment 6：
Separation recovery method and system, operating procedure for the heavy oil resources that handle carbonate containing mineral matter is as follows：
(1) oil-sand 15kg (carbonate content 55%, maximum particle diameter 3.5cm) the feedings mixing crushed by pulverizer A-anti-
Answer in device B with concentration is that the formic acid of 5 mol/Ls according to solid-liquid ratio is 1：3 (mass ratioes) are sufficiently mixed at 25 DEG C, reaction
30min, mixed reactor B are two-stage parallel connection, i.e., two-stage mixing reactor is alternately reacted operates with stratification.
Gained asphalt foam added after C degasification operation 5 times of quality pentane carry out separation of solid and liquid (two-stage settle with
Two-stage suspension separates D), moisture is less than 1.5% in separating obtained upper oil phase clear liquid, and solid content is less than 1.0%, into E
In separated, recycling design, while obtain pitch oil product 14, bitumen recovery rate 84.9%, asphaltenes are small in coal tar
In 3%.
(3) the lotion obtained by equipment for separating liquid from solid D and solid precipitation are sent to pickling reaction unit F washings, upper oil phase circulation
To equipment for separating liquid from solid D, the then individually extraction discharge of solid bituminite 16.
(4) waste liquid obtained by pickling reaction unit F and residue sandy soil precipitation add sodium hydroxide and are carried out in neutralization reaction device
Neutralization precipitation, then by filtering, by solid residue and precipitation filter out, resulting solution it is concentrated after add 5 times of volumes acetone into
Row dilution crystallization.
(5) the sediment in the sediment in mixed reactor B and the solution in pickling reaction unit F is in purification residual
With safety dumping after appropriate soda lye wash after being mixed in device J.
Final to obtain calcium formate purity 98.8%, residue solid is neutral.
One kind proposed by the present invention is rich in the separated system and method for carbonate heavy oil field, has passed through preferred embodiment
Be described, related technical personnel 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 (6)
- A kind of 1. separation recovery method for the heavy oil resources for being used to handle carbonate containing mineral matter, it is characterised in that operation step It is rapid as follows：Mink cell focus mineral first pass through pulverizer crushing, then with unitary acid solution hybrid reaction, obtain containing heavy oil whip, gas The mixture of body, calcium salt soln and residue；(2) heavy oil whip is diluted after degassing procedure using solvent, and the mixture after dilution is entered separation of solid and liquid system System carries out separation of solid and liquid, obtains solvent heavy oil mixture clear liquid, oil hydrosol and solid precipitation；(3) gained solvent heavy oil mixture clear liquid enters solvent recovering system by solvent recovery, while obtains hydrocarbon class composition； And oil hydrosol and solid precipitation then enter pickling system and carry out Reaction Separation；(4) pickling system produces gas, solvent naphtha, solution, asphalitine and sandy soil, gained solvent naphtha and is back to solid-liquid separation system, Asphalitine is individually extracted by enrichment；Step salting liquid and sandy soil residue that (4) pickling produces recycle product salt therein after filtering, react, crystallize；(1) residue mixture and step that step producesFiltering produce sandy soil residue discharge after alkali neutralization or again profit With；Handled heavy oil field is the heavy oil field rich in carbonate mine material, the mink cell focus rich in carbonate mine material Ore deposit is oil-sand, shale oil, landing oil or greasy filth；The step (1) in the acid solution of heavy oil field hybrid reaction be hydrobromic acid, formic acid, and acid solution pH value is less than 1；The step (2) in the solvent that is added be chain hydrocarbon solvent one or more of mixtures, addition is heavy oil vacuole 0.5 ~ 5 times of foam quality；The stepMiddle crystallization process is dilution crystallization process, and used dissolved agent is methanol, ethanol, ether or acetone, Its addition is 0.3 ~ 5 times of salting liquid volume.
- 2. the separation recovery method of the heavy oil resources according to claim 1 for being used to handle carbonate containing mineral matter, its It is characterized in that：The step (1) in hybrid reaction system be single-stage intermittent operation, or plural parallel stage alternating continous way behaviour Make, or plural serial stage continous way operation mixing reactor.
- 3. the separation recovery method of the heavy oil resources according to claim 1 for being used to handle carbonate containing mineral matter, its It is characterized in that：(2) middle solid-liquid separation system includes 1 ~ 3 grade of liquid and consolidates the centrifugal of gravitational settling system and 1 ~ 3 grade the step Piece-rate system.
- 4. the separation recovery method of the heavy oil resources according to claim 1 for being used to handle carbonate containing mineral matter, its It is characterized in that：The chain hydrocarbon solvent is pentane, hexane, heptane.
- 5. the separation recovery method of the heavy oil resources according to claim 1 for being used to handle carbonate containing mineral matter, its It is characterized in that：The stepMiddle reaction process is to add lye to carry out neutralization reaction and precipitation reaction, the lye added For sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide or limewash, stop the addition of lye when pH value of solution is more than 5.
- A kind of 6. separation mining system for the heavy oil resources for being used to handle carbonate containing mineral matter, it is characterised in that：Composition is such as Under：Breaker material outlet connects mixed reactor, and mixed reactor is also formed with liquid material import, liquid material Import connects acid solution storage tank, and mixed reactor is formed respectively with gas vent, foam outlet, liquid outlet and solid residue and goes 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 in connecting pipe, adds solvent, solid-liquid point From the oil phase outlet connection solvent recovery unit on device top, solvent enters equipment for separating liquid from solid together with the foam after degassing, The top oil phase of equipment for separating liquid from solid, which exports, connects solvent recovery unit, remaining coal tar after solvent recovery unit recycling design Oil product is gone to refine after discharge；The liquid of equipment for separating liquid from solid lower part connects pickling reaction unit with solid outlet, carries out hypo acid again Wash, the upper oil phase after pickling returns to equipment for separating liquid from solid, and gas vent is connected to gas recycling and processing device, the liquid of lower floor Filtration apparatus entrance is connected with sandy soil solid outlet, the asphalitine solid of generation is discharged through asphalitine outlet, and filtration apparatus is solid Body solid discharge connects purification residual device, filtration apparatus liquid outlet connection neutralization precipitation unit, neutralization precipitation unit lower part Precipitation outlet is formed with, neutralization precipitation unit liquid outlet connection crystalline substance device, crystallization apparatus is formed with dissolved agent import, is passed through dissolved Agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101421045A (en) * | 2006-03-07 | 2009-04-29 | 马拉松油砂美国有限公司 | Processing asphaltene-containing tailings |
| CN103693833A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Comprehensive control method of oily sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101421045A (en) * | 2006-03-07 | 2009-04-29 | 马拉松油砂美国有限公司 | Processing asphaltene-containing tailings |
| CN103693833A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Comprehensive control method of oily sludge |
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