CN106010620A - Separating and exploiting method and system for processing carbonate mineral substance containing heavy oil resources - Google Patents

Abstract

The invention relates to a separating and exploiting method for processing carbonate mineral substance containing heavy oil resources. The method is characterized by comprising the steps that the carbonate mineral substance containing heavy oil resources such as oil sand, oil shale and oily sludge are mixed with a prepared solution and a chemical additive for reacting under the certain condition, mineral substances in heavy oil deposit are dissolved, and then the purpose of separating heavy oil from mineral particles is achieved; the separated heavy oil is subjected to subsequent processing treatment to further remove entrained water and solid particles, and a clean heavy oil product is obtained; waste liquid and mineral substance precipitates which are generated in the previous process are recycled separately, and then harmless discharge is finally achieved. Therefore, not only is the heavy oil extracted out from the oil deposit effectively, but also energy sources are greatly saved, and the energy-saving and emission-reducing production purposes of normal-temperature extracting or heavy oil recycling are achieved.

Description

Mining method and system is separated for process the heavy oil resources of carbonate containing mineral

Technical field

The present invention relates to a kind of heavy oil resources for processing carbonate containing mineral separate mining method and System, belongs to chemical separating and reaction engineering technical field, be specifically related to crush, react, settle, filter, The methods such as distillation, crystallization.

Background technology

Heavy oil field (e.g., oil-sand, oil shale, landing oil, greasy filth etc.) be a kind of by mink cell focus (or Colophonium), The grains of sand, clay and the complex mixture of a small amount of water composition.Because its process is huge, it is increasingly becoming a kind of standby Petroleum resources.As a example by oil-sand, its proved reserves account for about 1/3rd of existing petroleum resources total amount, existing Have technologically recoverable reserves to be about 651,000,000,000 barrels, be mainly distributed on Canada, Venezuela, the U.S., Russia, The ground such as Indonesia and China, are a kind of very promising substitute energy source for petroleums.

The exploitation of oil-sand can be divided into strip mining transformation and in-situ extraction according to himself physicochemical property and geological conditions. For Canadian moisturizing type oil-sand, when mineral products buried depth is less than 75 meters, industrial main employing thermokalite Oil-sand is separated by washing process；And when oil-sand ore deposit buried depth is more than 75 meters, then use in-situ extraction Method, as to bottom inject vapours, hot solvent etc..But, for glossy property oil-sand, such as the U.S. still Oil-sand is dripped by the technique that his state oil-sand, Indonesia's oil-sand and Xinjiang, China oil-sand then cannot effectively utilize thermokalite to wash Green grass or young crops separates.Other new techniques many to this end, be born, as solvent extraction technology (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 technology have respective advantage, such as, molten Agent abstraction technique have extraction yield is high, extraction process need not water participation, can operate under room temperature, solvent can follow The advantages such as ring use；Pyrolysis technology can realize mink cell focus extraction and refine oil integrated process, decreases technique mistake Journey；What microbial fermentation technology can realize gentleness puies forward oil process etc..But, they are the most all along with each Shortcoming, the environmental problem revealed such as the solvent recovery problem in sand solid residual after solvent extraction and solvent, hot tearing The problem that in solution preocess, energy consumption is too high, the stability of fermentable and scale-up problems, these all make above-mentioned Technology runs into various resistance in the middle of course of industrialization, causes it to ultimately fail to industrially and realizes scale use.

For from mineral composition, it is divided into silicate to be main mineral intergrowth material with the mineral of heavy oil field symbiosis, Or the mineral based on carbonate.Above-mentioned all kinds of research is with for the heavy oil field rich in silicate, typically Such as Canada's oil-sand.And the mink cell focus for carbonate type (rich in calcium carbonate etc.) is exploited the most fewer, main If owing to the mink cell focus of this type is general and mineral has stronger active force, and making WATER-WASHING METHOD effect not Good.Use acid wash to process this type of heavy oil field, can effectively mineral component therein be dissolved, and not Affect the quality of mink cell focus, can preferably play the effect efficiently carrying oil.But, the weight that this technology faces The problem is wanted to be: production process to have substantial amounts of waste liquid produce, containing materials such as abundant calcium salt, iron salt in waste liquid. Therefore, solving wastewater problem in recovery process is also a main technical barrier.

As can be seen here, operating cost and environmental problem are the exploitations of current heavy oil field, the most glossy acid carbonate Class oil-sand, key technical problem.To this end, patent of the present invention will propose at a kind of mainly for the problems referred to above Manage the separation method of the heavy oil field rich in carbonate mine material.

Summary of the invention

It is an object of the invention to provide a kind of low cost, efficient, energy-conservation, may be used for processing rich in carbonate The mink cell focus ore resources of mineral, separating mining method and being such as oil-sand, shale oil, landing oil, greasy filth etc. System.

The present invention is realized by following equipment and technical scheme:

A kind of heavy oil resources for processing carbonate containing mineral separate mining method and system, its feature Being, operating procedure is as follows:

Mink cell focus mineral first pass through reducing mechanism pulverize, then with monoacid solution hybrid reaction, contained Mink cell focus foam, gas, calcium salt soln, residue mixture；

(2) mink cell focus foam is after degassing procedure, uses solvent dilution, and enters the mixture after dilution Equipment for separating liquid from solid carries out solid-liquid separation, it is thus achieved that solvent mink cell focus mixture clear liquid, oil hydrosol and Solid precipitation；

(3) gained solvent mink cell focus mixture clear liquid entrance solvent recovery unit is by solvent recovery, obtains weight simultaneously Matter oil product；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, and gained solvent naphtha is back to Equipment for separating liquid from solid, asphalitine individually extracts through enrichment；

(5) step (4) pickling produces saline solution and sandy soil residue reclaim therein after filtering, react, crystallizing Product salt；

(6) (5) the residue mixture that (1) step produces and step filter the sandy soil residue of generation in alkali and heel row Put or recycle.

And, handled heavy oil field is the heavy oil field rich in carbonate mine material, as oil-sand, shale oil, Landing oil, greasy filth.

And, described step (1) in be hydrobromic acid, formic acid with the acid solution of heavy oil field hybrid reaction, and acid is molten Liquid pH value is less than 1.

And, described step (1) in hybrid reaction system be single-stage intermittent operation, or plural parallel stage is alternately Continuous way operates, or plural serial stage continuous way operation mixing reactor.

And, described step (2) middle equipment for separating liquid from solid includes the liquid-solid gravity settling device and 1～3 of 1～3 grade The centrifugal separator of level.

And, described step (2) in the mixture of one or more that solvent is chain hydrocarbon solvent that added, add Enter that amount is heavy oil whip quality 0.5～5 times.

And, described chain hydrocarbon solvent is pentane, hexane, heptane.

And, described step (5) middle course of reaction is to add alkali liquor to be neutralized reaction and precipitation, added The alkali liquor entered is the alkaline solutions such as sodium hydroxide solution, potassium hydroxide solution, ammonia, lime water, works as solution The addition of alkali liquor is stopped when pH is more than 5.

And, described step (5) in crystallization process be dilution crystallization process, the dissolved agent used be methanol, Ethanol, ether, acetone and other organic solvent, its addition is 0.3～5 times of saline solution volume.

A kind of heavy oil resources for processing carbonate containing mineral separate mining method and system, composition is such as Under:

Breaker material outlet connects mixed reactor, and mixed reactor is also shaped with liquid material import, Liquid material import connects acid solution storage tank, and mixed reactor is formed respectively with gas outlet, foam outlet, liquid Outlet and solid residue outlet, foam outlet connects foam depassing unit, and liquid outlet connects pickling reaction dress Putting, solid residue outlet connects purification residual device, and foam depassing unit connects equipment for separating liquid from solid, is connecting Being shaped with solvent charge door on pipeline, add solvent, the oil phase outlet on equipment for separating liquid from solid top connects solvent recovery Device, solvent enters equipment for separating liquid from solid together with the foam after degassing, and the top oil phase of equipment for separating liquid from solid goes out Mouth connects solvent recovery unit, and after solvent recovery unit recycling design, remaining coal tar goes oil product refine after discharging； The liquid of equipment for separating liquid from solid bottom and solid outlet connect pickling reaction unit, carry out pickling again, after pickling Upper oil phase return equipment for separating liquid from solid, gas outlet is connected to gas recycling and processing device, the liquid of lower floor Connecting defecator entrance with sandy soil solid outlet, the asphalitine solid of generation is discharged through asphalitine outlet, mistake Filter device solid residue outlet connects purification residual device, and defecator liquid outlet connects neutralization precipitation unit, Neutralization precipitation unit bottom is shaped with precipitation outlet, and the outlet of neutralization precipitation unit liquid connects crystallization apparatus, crystallization dress Put and be shaped with dissolved agent import, be passed through dissolved agent.

The unique distinction following points of the present invention:

1, the present invention uses acid solution and richness carbonato heavy oil field to carry out hybrid reaction, and acid solution can By oil from grains of sand surface extractions out, oil and sand are totally separated from out, it is achieved reclaiming completely and the grains of sand of oil Harmless process, raw material is conveniently easy to get, simple to operate, and efficiency is high, reduces cost.

2, in mink cell focus froth treatment process of the present invention, acid wash is used to process, no emulsion and solid precipitation Only can well recycling design and oil, moreover it is possible to the heavy constituent in selective extraction mink cell focus, such as asphalitine etc., Decrease owing to the environmental problem caused arranged outward by solvent or oil, can also effectively prevent hydrocarbon class composition simultaneously The fouling or the blocking that occur in following process, poison the problems such as catalyst.

3, hybrid reaction system and pickling system are produced by the present invention solution and solid precipitation, use filter, Neutralize, precipitate and the mode that crystallize processes, the various useful components in effective recovery mineral so that process without Evilization is discharged, and reduces environmental protection treatment cost；And use the mode of dilution crystallization to effectively reduce energy consumption, carry High whole economic efficiency.

Accompanying drawing explanation

Fig. 1. for process carbonate containing mineral heavy oil resources separate mining method and system flow Figure

Stock number: 1. rich in carbonate heavy oil field；2. the heavy oil field after pulverizing；3. acid solution I (one Unit's acid)；4. gas I (carbon dioxide)；5. mink cell focus foam I；6. acid solution II (the remaining liquid of reaction)；7. Solid residue (sandy soil)；8. gas II (carbon dioxide)；9. mink cell focus foam II；10. solvent (chain hydrocarbon)； Mink cell focus foam after 11. dilutions；12. solvents-mink cell focus mixture；13. Solids-solution mixture；14. weights Matter oil product；15. recovered solvents；16. asphalitines；17. fresh acid solutions；18. gas III (dioxies Change carbon)；19. solidliquid mixtures；20. solvent-mink cell focus foam mixture；21. saline solution；22. filtering residues； 23. alkali liquor I；24. calcium salt solns；25. metal base compound precipitations；26. dissolved agent；27. water I；28. calcium salts； 29. alkali liquor 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 unit；F. pickling reaction unit；G. filter element；H. neutralization precipitation unit；I. crystallize Device；J. purification residual device.

Detailed description of the invention

Present invention provide for processing the separating mining method and be of heavy oil resources of carbonate containing mineral System, this separation method uses acid solution to react with heavy oil field, and after reaction, the mink cell focus foam of gained uses Solvent dilution and the process such as solid-liquid separation, pickling realize mink cell focus purification process；And gained waste reaction solution and precipitation Residue then use filtration, neutralize, precipitate, the method such as crystallization is separately recovered, finally realize mink cell focus and separate Extract and the purpose of by-product classification recovery.Use chain hydrocarbon to process heavy oil whip, be possible not only to reduce heavy Moisture in oil and mineral content, it is also possible to the heavy constituents such as asphalitine precipitated, improve mink cell focus and produce The quality of product.During to liquid and waste slag produced process, use and filter and chemical precipitation, the method for dilution crystallization, Not only all kinds of mineral compositions are separately recovered, and can also be the most energy-conservation.This piece-rate system and method Not only successfully mink cell focus and various mineral are efficiently separated recovery, and achieves economy, energy-conservation, high The operation purpose of effect.

Mink cell focus separation method rich in carbonate mine material of the present invention includes following main device: pulverize Machine, mixing reactor, depassing unit, sedimentation device, equipment for separating liquid from solid, distilling apparatus, defecator, Crystallization apparatus and material transfer equipment etc..

Its concrete operation step is as follows:

The richest carbonato heavy oil field 1 size-reduced machine A obtains the heavy oil field 2 after pulverizing after pulverizing, by Material conveyor delivers to carry out in mixing reactor device B hybrid reaction with monoacid solution 3, dissolves wherein Mineral grain, it is thus achieved that mink cell focus foam 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 titanium dioxide that depassing unit C will contain in foam Carbon gas 8 removes, and is subsequently adding solvent 10 and is diluted the mink cell focus foam 9 after degassing；After dilution Mink cell focus foam 11 enters equipment for separating liquid from solid D and is divided into oil phase clear liquid 12, oil hydrosol and solid bulk precipitation 13；Oil phase clear liquid extraction also enters solvent recovery unit E and separates, and recycling design 15 also obtains mink cell focus Product 14；

(3) after oil hydrosol and solid sediment 13 are discharged, entrance pickling reaction unit F carries out pickling processes, institute The acid used is liquid 6 and the mixture of fresh acid solution 17, gained upper strata more than the part in mixed reactor B Oil phase, part oil phase 20 is back to equipment for separating liquid from solid D and separates, another part heavy constituent solid 16, Such as asphalitine, then individually extraction processes, and this composition is relatively big, by it from coal tar to the viscosity influence of coal tar Separation can make product 14 quality of coal tar improve, and prevents the Colophonium of big viscosity from affecting rectification efficiency, impact dress Put the situation of inside；

The gas 18 of pickling reaction unit is discharged；The solution produced after pickling and sandy soil precipitation 19 are expelled to filter Unit G filters, it is thus achieved that the saline solution 21 without solid and filtering residue 22；

The most above-mentioned saline solution 21 is input in neutralization precipitation unit H, adds alkali liquor 23, removes metal alkalization Thing precipitation 25 (metal ions, such as ferrum, manganese, nickel, copper, magnesium etc.), gained calcium salt soln 24 is through concentrating After be input to crystallization apparatus I, add dissolved agent 26 and carry out dilution crystallization, it is thus achieved that calcium salt product 28, evaporate Water 27 reclaims；

(5) the precipitate 7 in mixed reactor joins purification residual device J with filtering residue 22 after mixing, and uses Residual sand 30 and water 31, safety dumping is obtained after suitable aqueous alkali 29 washing.Sand is reusable or sharp With.

The acid solution that the present invention uses is unitary organic acid or mineral acid, such as hydrobromic acid, formic acid etc., and acid solution PH value is less than 1.Described acid solution is 1:3-10 with the solid-to-liquid ratio of heavy oil field.

In the present invention, mixed reactor is single-stage intermittent operation, or plural parallel stage replaces continuous way operation, or Plural serial stage continuous way operation mixing reactor.

In the present invention, equipment for separating liquid from solid includes the liquid-solid gravity separator of 1～3 grade and 1～3 grade centrifugal Separator, separates such as centrifuge or suspension separates.

Liquid and waste slag produced process in the present invention can be to filter successively, react, filter, crystallize, or successively For the operation reacted, filter, crystallize.

Crystallization process in the present invention is dilution crystallization process, the dissolved agent used be methanol, ethanol, ether, Acetone and other organic solvent, its addition is 0.3～5 times of saline solution volume.

Rich in the core apparatus of separation and Extraction process of carbonate heavy oil field in the present invention, comprise five big main dresses Put: 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 dress Put, pickling reaction unit, defecator, neutralization reaction unit, crystallization apparatus, purification residual device and various Material transfer equipment and pipe-line equipment, concrete structure is as follows:

Breaker material outlet connects mixed reactor, and mixed reactor is also shaped with liquid material import, Liquid material import connects acid solution storage tank, and mixed reactor is formed respectively with gas outlet, foam outlet, liquid Outlet and solid residue outlet, foam outlet connects foam depassing unit, and liquid outlet connects pickling reaction dress Putting, solid residue outlet connects purification residual device, and foam depassing unit connects equipment for separating liquid from solid, is connecting Being shaped with solvent charge door on pipeline, add solvent, the oil phase outlet on equipment for separating liquid from solid top connects solvent recovery Device, solvent enters equipment for separating liquid from solid together with the foam after degassing, and the top oil phase of equipment for separating liquid from solid goes out Mouth connects solvent recovery unit, and after solvent recovery unit recycling design, remaining coal tar goes oil product refine after discharging； The liquid of equipment for separating liquid from solid bottom and solid outlet connect pickling reaction unit, carry out pickling again, after pickling Upper oil phase return equipment for separating liquid from solid, gas outlet is connected to gas recycling and processing device, the liquid of lower floor Connecting defecator entrance with sandy soil solid outlet, the asphalitine solid of generation is discharged through asphalitine outlet, mistake Filter device solid residue outlet connects purification residual device, and defecator liquid outlet connects neutralization precipitation unit, Neutralization precipitation unit bottom is shaped with precipitation outlet, and the outlet of neutralization precipitation unit liquid connects crystallization apparatus, crystallization dress Put and be shaped with dissolved agent import, be passed through dissolved agent.

The concrete operation step of process implementing:

Within the richest carbonato heavy oil field size-reduced machine A is crushed to 5cm, material conveyor deliver to Mixing reactor device B carries out hybrid reaction with concentration more than the acid solution of 0.1 mol/L.

(2) dissolved mink cell focus mineral grain, it is thus achieved that mink cell focus foam mixture, gas, solution and precipitation.

(3) the mink cell focus foam obtained is discharged into depassing unit C and is removed by the carbon dioxide contained in foam Go, be subsequently adding and be equivalent to the solvent of foam quality 0.5～5 times the foam after degasification is diluted.

(4) the foam entrance equipment for separating liquid from solid D after dilution is divided into oil phase clear liquid, oil hydrosol and solid to sink mutually Form sediment；Oil phase clear liquid extraction also enters solvent recovery unit and separates, and recycling design also obtains hydrocarbon class composition； Oil hydrosol and solid sediment enter pickling reaction unit F after discharging and carry out pickling processes, gained upper oil phase It is back to equipment for separating liquid from solid D separate, another part coal tar solid (asphalitine) then extraction conduct One of side-product.

(5) the solution and the precipitation that produce after pickling filter, it is thus achieved that without the solution of solid；Above-mentioned solution adds Entering alkali liquor and remove hetero atom, gained calcium salt soln concentrates.Solution after concentration adds dissolved agent and crystallizes, Obtain product.

(6) with suitable after the precipitate in mixed reactor mixes with the precipitate in the solution in descaling bath Safety dumping after soda lye wash.

Below, present invention following example are illustrated, but is not limited to following example.

Embodiment 1:

Separating mining method and system for process the heavy oil resources of carbonate containing mineral, operating procedure is such as Under:

(1) the oil-sand 15kg (carbonate content 42%, maximum particle diameter 0.5cm) pulverized through pulverizer A send Entering in mixing-reactor B with the hydrobromic acid that pH is 1 according to solid-to-liquid ratio is that 1:30 (mass ratio) is under room temperature It is sufficiently mixed and reacts 1 hour.

(2) gained asphalt foam heptane of 0.5 times of quality of addition after C degasification operates carries out solid-liquid separation ( Level sedimentation and first-stage centrifugal D), in separating obtained upper oil phase clear liquid, moisture is less than 3.5%, and solid content is little In 1.5%, enter in E and separate, recycling design, obtain coal tar product 14 simultaneously, coal tar reclaims Rate 79.3%, coal tar studies on asphaltene content is less than 10%.

(3) emulsion and the solid precipitation of equipment for separating liquid from solid D gained is sent to pickling reaction unit F washing, upper strata Oil phase is recycled to equipment for separating liquid from solid D, and solid bituminite 16 the most individually extracts discharge.

(4) pickling reaction unit F gained waste liquid and residue sandy soil precipitation are after G filters, and add sodium hydroxide It is neutralized precipitation in neutralizing in reaction unit H, tan precipitate is leached, add after gained solution is concentrated The ether of 0.3 times of volume carries out dilution crystallization.

(5) the precipitate in mixed reactor B and the precipitate in the solution in pickling reaction unit F are residual With safety dumping after suitable soda lye wash after mixing in slag purifier J.

Final acquisition calcium bromide crystal purity 99.3%, hydrated ferric oxide. content 93.5% in tan precipitate, residue is solid Body is neutral.

Embodiment 2:

Separating mining method and system for process the heavy oil resources of carbonate containing mineral, operating procedure is such as Under:

(1) the oil-sand 15kg (carbonate content 61%, maximum particle diameter 5cm) pulverized through pulverizer A sends into mixed Conjunction-reactor B is that 1:3 (mass ratio) is in room temperature with the hydrobromic acid that concentration is 2 mol/L according to solid-to-liquid ratio Under be sufficiently mixed, react 120min.

(2) gained asphalt foam heptane of 5 times of quality of addition after C degasification operates carries out solid-liquid separation ( Level sedimentation and three grades of centrifugal D), in separating obtained upper oil phase clear liquid, moisture is less than 1.5%, and solid content is little In 1.5%, enter in E and separate, recycling design, obtain coal tar product 14 simultaneously, coal tar reclaims Rate 85.2%, coal tar studies on asphaltene content is less than 5%.

(3) emulsion and the solid precipitation of equipment for separating liquid from solid D gained is sent to pickling reaction unit F washing, upper strata Oil phase is recycled to equipment for separating liquid from solid D, and solid bituminite 16 the most individually extracts discharge.

(4) pickling reaction unit F gained waste liquid and residue sandy soil precipitation are after G filters, and add sodium hydroxide It is neutralized precipitation in neutralizing in reaction unit H, tan precipitate is leached, after gained solution is concentrated, add 2 The ether of times volume carries out dilution crystallization.

(5) the precipitate in mixed reactor B and the precipitate in the solution in pickling reaction unit F are residual With safety dumping after suitable soda lye wash after mixing in slag purifier J.

Final acquisition calcium bromide crystal purity 99.4%, hydrated ferric oxide. content 94.2% in tan precipitate, residue is solid Body is neutral.

Embodiment 3:

Separating mining method and system for process the heavy oil resources of carbonate containing mineral, operating procedure is such as Under:

(1) the greasy filth 15kg (carbonate content 56%, maximum particle diameter 1.5cm) pulverized through pulverizer A sends into Mixing-reactor B is that 1:3 (mass ratio) is in often with the formic acid that concentration is 3 mol/L according to solid-liquid ratio It is sufficiently mixed under temperature, reacts 120min.

(2) gained asphalt foam pentane of 3 times of quality of addition after C degasification operates carries out solid-liquid separation (two Level sedimentation and three grades of suspension D), in separating obtained upper oil phase clear liquid, moisture is less than 1.5%, and solid content is little In 1.5%, enter in E and separate, recycling design, obtain coal tar product 14 simultaneously, coal tar reclaims Rate 82.5%, coal tar studies on asphaltene content is less than 3.5%.

(3) emulsion and the solid precipitation of equipment for separating liquid from solid D gained is sent to pickling reaction unit F washing, upper strata Oil phase is recycled to equipment for separating liquid from solid D, and solid bituminite 16 the most individually extracts discharge.

(4) pickling reaction unit F gained waste liquid and residue sandy soil precipitation are after G filters, and add sodium hydroxide It is neutralized precipitation in neutralizing in reaction unit H, tan precipitate is leached, after gained solution is concentrated, add 5 The ethanol of times volume carries out dilution crystallization.

(5) the precipitate in mixed reactor B and the precipitate in the solution in pickling reaction unit F are residual With safety dumping after suitable soda lye wash after mixing in slag purifier J.

Final acquisition calcium formate crystal purity 97.3%, hydrated ferric oxide. content 93.5% in tan precipitate, residue is solid Body is neutral.

Embodiment 4:

Separating mining method and system for process the heavy oil resources of carbonate containing mineral, operating procedure is such as Under:

(1) the oil shale 15kg (carbonate content 52%, maximum particle diameter 5cm) pulverized through pulverizer A sends into Mixing-reactor B is that 1:3 (mass ratio) is in 65 DEG C with the formic acid that concentration is 5 mol/L according to solid-liquid ratio Lower mixing, reaction 30min, mixed reactor B be two-stage series connection, i.e. one-level be hybrid reaction, another Level is flotation.

(2) gained asphalt foam hexane of 5 times of quality of addition after C degasification operates carries out solid-liquid separation (two Level sedimentation separates D with two-stage suspension), in separating obtained upper oil phase clear liquid, moisture is less than 1.2%, admittedly contain Amount, less than 1.5%, enters in E and separates, recycling design, obtains coal tar product 14, coal tar simultaneously The response rate 85.7%, coal tar studies on asphaltene content is less than 3%.

(3) emulsion and the solid precipitation of equipment for separating liquid from solid D gained is sent to pickling reaction unit F washing, upper strata Oil phase is recycled to equipment for separating liquid from solid D, and solid bituminite 16 the most individually extracts discharge.

(4) pickling reaction unit F gained waste liquid and residue sandy soil precipitation are after G filters, and add sodium hydroxide It is neutralized precipitation in neutralizing in reaction unit H, tan precipitate is leached, after gained solution is concentrated, add 5 The acetone of times volume carries out dilution crystallization.

(5) the precipitate in mixed reactor B and the precipitate in the solution in pickling reaction unit F are residual With safety dumping after suitable soda lye wash after mixing in slag purifier J.

Final acquisition calcium formate purity 97.5%, hydrated ferric oxide. content 93.2% in tan precipitate, in residue solid Property.

Embodiment 5:

Separating mining method and system for process the heavy oil resources of carbonate containing mineral, operating procedure is such as Under:

(1) the oil-sand 15kg (carbonate content 52%, maximum particle diameter 3cm) pulverized through pulverizer A sends into mixed Conjunction-reactor B is that 1:6 (mass ratio) is in 25 DEG C with the formic acid that concentration is 1 mol/L according to solid-liquid ratio Under be sufficiently mixed, reaction 30min, mixed reactor B be two-stage parallel connection, i.e. two-stage mixing reactor hand over For carrying out reaction and stratification operation.

(2) gained asphalt foam adds hexane and the heptane mixture (body of 5 times of quality after C degasification operates Long-pending ratio is 1:1) carry out solid-liquid separation (two-stage sedimentation separates D with two-stage suspension), separating obtained upper oil phase is clear In liquid, moisture is less than 2.5%, and solid content is less than 1.5%, enters in E and separates, recycling design, with Time obtain coal tar product 14, the coal tar response rate 87.2%, in coal tar asphaltenes be less than 6.5%.

(3) emulsion and the solid precipitation of equipment for separating liquid from solid D gained is sent to pickling reaction unit F washing, upper strata Oil phase is recycled to equipment for separating liquid from solid D, and solid bituminite 16 the most individually extracts discharge.

(4) pickling reaction unit F gained waste liquid and residue sandy soil precipitation are after G filters, and add sodium hydroxide It is neutralized precipitation in neutralizing in reaction unit H, tan precipitate is leached, after gained solution is concentrated, add 5 The acetone of times volume carries out dilution crystallization.

(5) the precipitate in mixed reactor B and the precipitate in the solution in pickling reaction unit F are residual With safety dumping after suitable soda lye wash after mixing in slag purifier J.

The final calcium formate purity 98.9% that obtains, residue solid neutrality.

Embodiment 6:

Separating mining method and system for process the heavy oil resources of carbonate containing mineral, operating procedure is such as Under:

(1) the oil-sand 15kg (carbonate content 55%, maximum particle diameter 3.5cm) pulverized through pulverizer A sends into Mixing-reactor B is that 1:3 (mass ratio) is in 25 DEG C with the formic acid that concentration is 5 mol/L according to solid-liquid ratio Under be sufficiently mixed, reaction 30min, mixed reactor B be two-stage parallel connection, i.e. two-stage mixing reactor hand over For carrying out reaction and stratification operation.

(2) gained asphalt foam pentane of 5 times of quality of addition after C degasification operates carries out solid-liquid separation (two Level sedimentation separates D with two-stage suspension), in separating obtained upper oil phase clear liquid, moisture is less than 1.5%, admittedly contain Amount, less than 1.0%, enters in E and separates, recycling design, obtains coal tar product 14 simultaneously, and Colophonium returns Yield 84.9%, in coal tar, asphaltenes is less than 3%.

(3) emulsion and the solid precipitation of equipment for separating liquid from solid D gained is sent to pickling reaction unit F washing, upper strata Oil phase is recycled to equipment for separating liquid from solid D, and solid bituminite 16 the most individually extracts discharge.

(4) pickling reaction unit F gained waste liquid and residue sandy soil precipitation add sodium hydroxide in neutralizing reaction unit In be neutralized precipitation, then through filtering, solid residue and precipitation are leached, add after gained solution is concentrated The acetone of 5 times of volumes carries out dilution crystallization.

(5) the precipitate in mixed reactor B and the precipitate in the solution in pickling reaction unit F are residual With safety dumping after suitable soda lye wash after mixing in slag purifier J.

The final calcium formate purity 98.8% that obtains, residue solid neutrality.

A kind of system and method separated rich in carbonate heavy oil field that the present invention proposes, by preferably implementing Example is described, and person skilled substantially can be to this in without departing from present invention, spirit and scope Structure described in literary composition and technical method is modified or suitably changes and combines, realizes the technology of the present invention.Especially It is pointed out that all similar replacements and change apparent to those skilled in the art, They are considered as being included in present invention spirit, scope and content.

Claims (10)

1. for process carbonate containing mineral heavy oil resources separate a mining method, its feature exists In, operating procedure is as follows:

Mink cell focus mineral first pass through pulverizer pulverize, then with monoacid solution hybrid reaction, obtain containing heavy Oil whip, gas, calcium salt soln, residue mixture；

(2) mink cell focus foam is after degassing procedure, uses solvent dilution, and enters solid by the mixture after dilution Liquid separation system carries out solid-liquid separation, it is thus achieved that solvent mink cell focus mixture clear liquid, oil hydrosol and solid precipitation；

(3) gained solvent mink cell focus mixture clear liquid entrance solvent recovering system is by solvent recovery, obtains heavy simultaneously Oil product；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, and gained solvent naphtha is back to solid Liquid separation system, asphalitine individually extracts through enrichment；

(5) step (4) pickling produces saline solution and sandy soil residue reclaim therein after filtering, react, crystallizing Product salt；

(6) (5) the residue mixture that (1) step produces and step filter the sandy soil residue of generation in alkali and heel row Put or recycle.

Separating of heavy oil resources for processing carbonate containing mineral the most according to claim 1 Mining method, it is characterised in that: handled heavy oil field is the heavy oil field rich in carbonate mine material, such as oil Sand, shale oil, landing oil, greasy filth.

Separating of heavy oil resources for processing carbonate containing mineral the most according to claim 1 Mining method, it is characterised in that: described step (1) in be hydrobromic acid, first with the acid solution of heavy oil field hybrid reaction Acid, and acid solution pH value is less than 1.

Separating of heavy oil resources for processing carbonate containing mineral the most according to claim 1 Mining method, it is characterised in that: described step (1) in hybrid reaction system be single-stage intermittent operation, or many Level alternately continuous way operation in parallel, or plural serial stage continuous way operation mixing reactor.

Separating of heavy oil resources for processing carbonate containing mineral the most according to claim 1 Mining method, it is characterised in that: described step (2) middle solid-liquid separation system includes the liquid-solid gravitational settling of 1～3 grade System and the centrifugal separation system of 1～3 grade.

Separating of heavy oil resources for processing carbonate containing mineral the most according to claim 1 Mining method, it is characterised in that: described step (2) in added solvent is chain hydrocarbon solvent one or more Mixture, addition is 0.5～5 times of heavy oil whip quality.

Separating of heavy oil resources for processing carbonate containing mineral the most according to claim 1 Mining method, it is characterised in that: described chain hydrocarbon solvent is pentane, hexane, heptane.

Separating of heavy oil resources for processing carbonate containing mineral the most according to claim 1 Mining method, it is characterised in that: described step (5) middle course of reaction is to add alkali liquor to be neutralized reaction and precipitation Reaction, the alkali liquor added is the alkaline solutions such as sodium hydroxide solution, potassium hydroxide solution, ammonia, lime water, The addition of alkali liquor is stopped when pH value of solution is more than 5.

Separating of heavy oil resources for processing carbonate containing mineral the most according to claim 1 Mining method, it is characterised in that: described step (5) middle crystallization process is dilution crystallization process, the dissolved used Agent is methanol, ethanol, ether, acetone and other organic solvent, and its addition is 0.3～5 times of saline solution volume.

10. for process carbonate containing mineral heavy oil resources separate an extraction system, its feature exists In: form as follows:

Breaker material outlet connects mixed reactor, and mixed reactor is also shaped with liquid material import, Liquid material import connects acid solution storage tank, and mixed reactor is formed respectively with gas outlet, foam outlet, liquid Outlet and solid residue outlet, foam outlet connects foam depassing unit, and liquid outlet connects pickling reaction dress Putting, solid residue outlet connects purification residual device, and foam depassing unit connects equipment for separating liquid from solid, is connecting Being shaped with solvent charge door on pipeline, add solvent, the oil phase outlet on equipment for separating liquid from solid top connects solvent recovery Device, solvent enters equipment for separating liquid from solid together with the foam after degassing, and the top oil phase of equipment for separating liquid from solid goes out Mouth connects solvent recovery unit, and after solvent recovery unit recycling design, remaining coal tar goes oil product refine after discharging； The liquid of equipment for separating liquid from solid bottom and solid outlet connect pickling reaction unit, carry out pickling again, after pickling Upper oil phase return equipment for separating liquid from solid, gas outlet is connected to gas recycling and processing device, the liquid of lower floor Connecting defecator entrance with sandy soil solid outlet, the asphalitine solid of generation is discharged through asphalitine outlet, mistake Filter device solid residue outlet connects purification residual device, and defecator liquid outlet connects neutralization precipitation unit, Neutralization precipitation unit bottom is shaped with precipitation outlet, and the outlet of neutralization precipitation unit liquid connects crystallization apparatus, crystallization dress Put and be shaped with dissolved agent import, be passed through dissolved agent.