CN105925297A - Method for separating heavy oil ore containing rich carbonate - Google Patents

Abstract

The invention relates to a method for separating heavy oil ore containing rich carbonate. Heavy oil resources, such as oil sand, oil shale and oily sludge, containing carbonate mineral substances are mixed with a prepared solution and a chemical additive under certain conditions, a reaction occurs, carbonate in the heavy oil ore is converted, and thus the target of separating heavy oil and mineral particles is achieved; a crude heavy oil product, an aqueous solution containing various rich metal ions and mineral substances used for building materials are obtained in the end of the separating process. By means of the technology, heavy oil can be effectively extracted from ore, and mineral substances such as metal ions in heavy oil ore can be recycled to a great extent; energy resources are greatly saved, and the purpose of energy-saving production of heavy oil normal-temperature extracting or recycling is achieved.

Description

A kind of separation method rich in carbonate heavy oil field

Technical field

The present invention relates to a kind of from rich in carbonate heavy oil field is isolated the separation method of mink cell focus, belonging to Work point from and reaction engineering technical field, be specifically related to crush, react, carry, the method such as flotation.

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 reserves are 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, 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 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.

As can be seen here, operating cost and environmental problem are the exploitations of current heavy oil field, the most glossy property oil-sand, Key technical problem.To this end, patent of the present invention will propose one process rich in carbon mainly for the problems referred to above The separation method of the heavy oil field of hydrochlorate mineral.

Summary of the invention

It is an object of the invention to provide a kind of low cost, efficiently, environmental protection, energy-conservation, may be used for processing rich in The heavy oil field of carbonate mine material, such as oil-sand, shale oil, landing oil, greasy filth etc., separation method, should Method is possible not only to extract the oil in heavy oil field, and can reclaim mineral values therein, Realize Green production process.

The technical scheme that the present invention realizes purpose is as follows:

A kind of separation method rich in carbonate heavy oil field: heavy oil field mixes in mixing channel with acid solution Merge reaction, obtain the foam mixture containing mink cell focus, mineral grain, bubble and water, aqueous solution and solid Precipitate.

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

And, described carbonate content exceedes the 10% of raw ore mineral content.

And, described heavy oil field is direct material or within pulverizer is crushed to particle diameter 10 centimetres.

And, described is binary or the organic acid of ternary or mineral acid with heavy oil field hybrid reaction acid solution A kind of acid or the mixed liquor of several acid, and acid solution pH value is less than 1.

And, described hybrid reaction temperature is 5～95 DEG C；Within the hybrid reaction time is 2 hours；Mixing Mode is stirring, ultrasonic, microwave etc..

And, the solution that reaction is obtained is the aqueous solution rich in metal ions such as ferrum, calcium, magnesium, aluminum.

And, the solid sediment that reaction is obtained is the collection containing mineral such as polynary hydrochlorate, silicate and clays Close.

A kind of separation method rich in carbonate heavy oil field, step is as follows:

The richest carbonato size-reduced machine of heavy oil field forms less granule after pulverizing, material conveyor send Hybrid reaction is carried out with acid solution to mixing reactor；

The most reacted liquid-solid mixed serum is delivered to flotation cell and carries out flotation layering；The direct extraction of gaseous product, The mink cell focus foam on upper strata is discharged by upper outlet, middle saline solution part circulation, and outside another part, row processes, The residue mineral discharge of bottom processes, and residue mineral includes part calcium precipitation and the undissolved grains of sand, surplus Remaining acid solution is circulated recycling.

Beneficial effects of the present invention following points:

(1) the method that the present invention uses mineral classification, selects suitable isolation technics to separate heavy oil field thing, Can not only effectively reduce separating difficulty, and can be efficiently modified in terms of energy consumption, environmental protection and break through, fall Low cost.

(2) the present invention uses single acid solution and richness carbonato heavy oil field to carry out hybrid reaction, generates Mink cell focus foam, gas, heavy metallic salt solution and the grains of sand easily reclaimed, separate very convenient fast, effect Very notable, raw material is conveniently easy to get, simple to operate.

(3) the present invention uses the means such as ultrasonic, microwave, stirring to strengthen heavy oil field separation process, permissible Effectively accelerate course of reaction, improve extraction efficiency.

(4) the mineral with mink cell focus symbiosis is converted into precipitate, convenient separation by the present invention, improves mineral Added value.

Accompanying drawing explanation

Fig. 1. a kind of method flow diagram processing carbonate containing heavy oil ore deposit

Stock number: 1. rich in carbonate heavy oil field；2. the heavy oil field after pulverizing；3. acid solution；4. weight Matter oil whip；5. aqueous solution；6. residue mineral

Device is numbered: A. reducing mechanism；B. mixed reactor.

A kind of continuous separating system rich in carbonate heavy oil field of Fig. 2 and method flow diagram ()

Stock number: 2-1. is rich in carbonate heavy oil field；Heavy oil field after 2-2. pulverizing；2-3. it is fresh Acid solution；2-4. feeds acid solution；The liquid-solid mixed serum of 2-5.；2-6. gaseous product；2-7. asphalt foam； 2-8. aqueous solution；2-9. residue mineral；2-10. recycle acid solution

Device is numbered: 2-A. reducing mechanism；2-B. mixed reactor；2-C. flotation unit.

Detailed description of the invention

The invention provides a kind of method separated for rich carbonato heavy oil field, this separation method uses Acid solution reacts with heavy oil field, realizes the purpose of mink cell focus separation and Extraction.This separation method not only becomes Being extracted from mineral by mink cell focus of merit, it is also possible to carry out part mineral converting and reclaim, obtains high attached Value added chemical products, it is achieved that efficiently, environmental protection, energy-conservation operation purpose.

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

It is to provide solid-liquid rich in the core system of the separation and Extraction process of carbonate heavy oil field contact and carry out anti- The place answered, i.e. mixing-reaction unit.Heavy oil field is crushed to certain particle diameter according to technical specification, by Conveyer is delivered in mixing-reaction unit mix with acid solution and react.Said process finally makes weight Matter oil from ore deposit separating flotation out, simultaneously, part mineral is converted into the higher chemicals of added value It is precipitated out, or is dissolved in solution.

The concrete operation step of process implementing:

(1) from mining area or the heavy oil field of mineral reserve zone (such as oil-sand mine, oil field, oilfield treatments factory etc.) Resource first passes through within pulverizer A is crushed to 10cm；

(2) the heavy oil field after pulverizing is molten with a certain proportion of acid in material conveyor sends into mixing-reactor Liquid, at 5～95 DEG C, carries out the hybrid reaction within 2 hours, then stands separatory, by supernatant heavy Matter oil whip takes out and carries out following process process, the aqueous solution simultaneously produced and the solid sediment of reactor bottom Separately process.

Mink cell focus separation method rich in carbonate mine material of the present invention includes following main device: pulverize Device, mixed reactor, material conveyor and equipment for liquid transportation etc..

Its concrete operation step is as follows:

Rich carbonato heavy oil field 1 size-reduced machine A forms little granule heavy oil field 2, by material after pulverizing Conveyer is delivered to carry out hybrid reaction with acid solution 3 in mixing reactor B；After reaction terminates, Jing Guojing Put layering, it is thus achieved that mink cell focus foam mixture 4, aqueous solution 5 and solid sediment 6, also portion gas, Because acid and carbonate reaction, produce carbon dioxide.Solid sediment is calcium precipitation and the part grains of sand, water-soluble Liquid be after polyprotic acid reacts with oil field produce the solution containing many kinds of metal ions, the metal of recyclable the inside from Son, accomplishes not discharge any heavy metal.Mink cell focus foam mixture can obtain mink cell focus after carrying out solvent recovery Product.

Hybrid reaction temperature employed in the present invention is 5～95 DEG C；Within the hybrid reaction time is 2 hours； Hybrid mode is stirring, ultrasonic, microwave etc..

The one that acid solution is binary or the organic acid of ternary or mineral acid that the present invention uses is sour or several acid Mixed liquor, such as sulphuric acid, oxalic acid, phosphoric acid etc. and relevant mixed liquor, and acid solution pH value is not more than 1.

Heavy oil field handled in the present invention is that (carbonate content is or not the heavy oil field rich in carbonate mine material Less than mineral total amount 10%), such as oil-sand, shale oil, landing oil, greasy filth etc..

For Fig. 2, use serial operation, specifically comprise the following steps that

The richest carbonato heavy oil field 2-1 size-reduced machine 2-A forms less granule 2-2 after pulverizing, by Material conveyor deliver in mixing reactor 2-B with acid solution 2-4 (fresh acid solution 2-3 and recycle acid solution The mixture of 2-10) carry out hybrid reaction；

The most reacted liquid-solid mixed serum 2-5 is delivered to flotation cell 2-C and carries out flotation layering；Gaseous product The direct extraction of 2-6, the mink cell focus foam 2-7 on upper strata is discharged by upper outlet, a middle saline solution 2-8 part Circulation, outside another part, row processes, and the residue mineral 2-9 discharge of bottom processes, and residue mineral includes portion Dividing calcium precipitation and the undissolved grains of sand, the 2-10 of remaining recycle acid solution is circulated recycling.

The fresh acid solution of acid solution is 2-3, can add circulation with survey line when joining in mixed reactor Acid solution 2-10, so using new label 2-4 to illustrate.

Operating procedure is as follows:

The core system being continuously separated extraction process rich in carbonate heavy oil field is made up of two parts: provide solid -liquid contacts and carries out the place reacted, i.e. mixed reactor, Gu fill with the flotation realizing oil-water-three-phase layering Put.Heavy oil field is crushed to certain particle diameter according to technical specification, conveyer be delivered to mixed reactor B mixes with acid solution and reacts.Reacted serosity is delivered to flotation unit 2-C by conveying equipment and enters Row flotation hierarchical operations, floats on that the mink cell focus of top layer is consecutive is discharged by upper outlet, the acid solution one that unreacted is complete Part is recycled in reactor, arranges outside another part, is sunken to bottom solid and is discharged by bottom.

The concrete operation step of process implementing:

Mink cell focus ore resources 1 from mining area or mineral reserve zone (such as oil field, oilfield treatments factory etc.) first passes through Reducing mechanism A pulverizes, the heavy oil field after pulverizing through material conveyor send in mixed reactor B with A certain proportion of acid solution, at 5～95 DEG C, carries out hybrid reaction.The serosity that hybrid reaction obtains is by delivery system System is delivered in flotation unit 2-C carry out flotation, layering, and the mink cell focus foam at flotation cell top is constantly by upper Outlet is discharged, and the solid sediment of bottom is discharged by bottom slag discharge, and the mutually a part of discharge of intermediate solution processes, A part is recycled in mixing-reaction unit.The gas that process produces is discharged by top gas outlet.

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

Embodiment 1:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

The oil-sand 5kg (carbonate content 45%, maximum particle diameter 5cm) pulverized through pulverizer A sends into mixed Close in reaction unit B with the sulphuric acid that pH is 1 according to solid-to-liquid ratio be 1:30 (mass ratio) under room temperature, fill Divide stirring mixing and react 1 hour, standing 20min and upper strata asphalt foam is taken out.

The extraction rate reached 99.5% of gained asphalt foam, in foam, solid sand grains and the clay of residual are total less than foam The 50% of quality, water content less than foam gross mass 15%, metal ion in solution concentration summation more than 1g/kg, Solid sediment about 0.55kg.

Embodiment 2:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

The oil-sand 5kg (carbonate content 10%, maximum particle diameter 0.5cm) pulverized through pulverizer A sends into Mixing-reactor B is that 1:3 (mass ratio) is in 55 DEG C with the phosphoric acid that concentration is 2 mol/L according to solid-liquid ratio Under be sufficiently mixed, ultrasonic reaction 120min, stand 2min by upper strata asphalt foam take out.

The extraction rate reached 99.7% of gained asphalt foam, in foam, solid sand grains and the clay of residual are total less than foam The 25% of quality, water content is less than the 35% of foam gross mass, and metal ion in solution concentration summation is more than 0.8 G/100ml, solid sediment about 1.9kg.

Embodiment 3:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

The Indonesia oil-sand 5kg (carbonate content 52%, maximum particle diameter 10cm) pulverized through pulverizer A send Enter in mixing-reactor B with the sulphuric acid that concentration is 5 mol/L according to solid-liquid ratio be 1:2 (mass ratio) in It is sufficiently mixed at 95 DEG C, stirring, reacts 60min, stand 20min and upper strata asphalt foam is taken out.

The bitumen extraction rate of gained asphalt foam reaches 99.5%, and in foam, solid sand grains and the clay of residual are less than bubble The 55% of foam gross mass, water content is less than the 25% of foam gross mass, and metal ion in solution concentration summation surpasses Cross 5g/100ml, solid sediment about 1.75kg.

Embodiment 4:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

The oil shale 5kg (carbonate content 25%, maximum particle diameter 6cm) pulverized through pulverizer A sends into Mixing-reactor B is that 1:3 (mass ratio) is in 65 DEG C with the oxalic acid that concentration is 4 mol/L according to solid-liquid ratio Lower mixing, ultrasonic reaction 30min, stand 10min and upper strata asphalt foam is taken out.

The mink cell focus extraction rate reached 99.5% of gained asphalt foam, in foam, solid sand grains and the clay of residual are less than The 45% of foam gross mass, water content is less than the 20% of foam gross mass, metal ion in solution concentration summation More than 3g/100ml, solid sediment about 1.6kg.

Embodiment 5:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

Through pulverizer A pulverize greasy filth 5kg (carbonate content 15%, maximum particle diameter 3cm) send into mixing- In reactor B with the sulphuric acid that concentration is 5 mol/L and Fluohydric acid. (coordinating according to the volume ratio of 1:2) according to Solid-liquid ratio is that 1:6 (mass ratio) is sufficiently mixed at 25 DEG C, ultrasonic reaction 40min, stands 25min Upper strata asphalt foam is taken out.

The extraction rate reached 99.8% of gained asphalt foam, in foam, solid sand grains and the clay of residual are total less than foam The 45% of quality, water content is less than the 20% of foam gross mass, and metal ion in solution concentration summation is more than 5 G/100ml, solid sediment about 1.5kg.

Embodiment 6:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

The Indonesia oil-sand 5kg (carbonate content 55%, maximum particle diameter 0.5cm) pulverized through pulverizer A sends into Mixing-reactor B is 1:2 (quality with the mixture of the sulphuric acid that concentration is 5 mol/L according to solid-liquid ratio Than) be sufficiently mixed at 5 DEG C, microwave reinforced reaction 50min, stand 25min and upper strata asphalt foam is taken Go out.

The extraction rate reached 99.5% of gained asphalt foam, in foam, solid sand grains and the clay of residual are total less than foam The 45% of quality, water content is less than the 32% of foam gross mass, and metal ion in solution concentration summation is more than 5 G/100ml, solid sediment about 0.5kg.

Embodiment 7:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

Through pulverizer A pulverize oil-sand (carbonate content 25%, maximum particle diameter 0.5cm) with 5kg/min The sulphuric acid sent in mixing-reactor B with 3 moles every liter of speed be 1:3 (mass ratio) according to solid-to-liquid ratio Being sufficiently mixed under room temperature, ultrasonic reaction, the serosity after stirring is delivered to flotation in flotation cell, by upper strata Colophonium Foam takes out；Middle solution returns in hybrid reaction groove according to 100kg/min, and remaining solution is with about 50kg/min discharges for other use；The precipitate being positioned at bottom is then discharged by bottom discharging mouth, such as Fig. 2 Shown in.The response rate of gained asphalt foam reaches 99.5%, and in foam, solid sand grains and the clay of residual are less than foam The 65% of gross mass, water content is less than the 15% of foam gross mass.Outer row's metal ion in solution concentration is the lowest In 10mg/kg

Embodiment 8:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

As in figure 2 it is shown, Indonesia's oil-sand (carbonate content 55%, the maximum particle diameter pulverized through pulverizer A 1.5cm) with the speed of 5kg/min send in mixing-reactor B with the phosphoric acid solution that concentration is 2 mol/L It is that 1:3 (mass ratio) is sufficiently mixed at 45 DEG C according to solid-liquid ratio；Serosity continuous print after ultrasonic reaction is defeated Go out to flotation cell C, carry out flotation.Solution in the middle of flotation cell C loops back in reactor with 10kg/min.

The response rate of gained asphalt foam reaches 98.5%, and in foam, solid sand grains and the clay of residual are total less than foam The 30% of quality, water content is less than the 28% of foam gross mass.Outer row's metal ion in solution concentration is not less than 3 g/kg。

Embodiment 9:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

As in figure 2 it is shown, oil shale (carbonate content 37.6%, the maximum particle diameter pulverized through pulverizer A 10cm) with the speed of 5kg/min send in mixing-reactor B with the oxalic acid that concentration is 5 mol/L according to Solid-liquid ratio is 1:6 (mass ratio) hybrid reaction at 95 DEG C；The output of reacted serosity continuous print is to floating Select and groove C carries out flotation.Solution in the middle of flotation cell C loops back in reactor with 27kg/min.

The extraction rate reached 99.8% of gained asphalt foam, in foam, solid sand grains and the clay of residual are total less than foam The 68% of quality, water content is less than the 20% of foam gross mass.Outer row's metal ion in solution concentration is not less than 25 mg/kg。

Embodiment 10:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

As in figure 2 it is shown, Indonesia's oil-sand (carbonate content 56%, the maximum particle diameter pulverized through pulverizer A 3cm) with the speed of 5kg/min send in mixing-reactor B with the sulphuric acid that concentration is 3 mol/L according to solid- Liquor ratio is that 1:6 (mass ratio) is sufficiently mixed at 5 DEG C；Meanwhile, will be equivalent to oil-sand ore deposit medium pitch The gasoline of content 100% (mass ratio) joins in reactor, and the serosity continuous print after ultrasonic reaction exports extremely Flotation cell C carries out flotation.Solution in the middle of flotation cell C loops back in reactor with 20kg/min.

The extraction rate reached 99.8% of gained asphalt foam, in foam, solid sand grains and the clay of residual are total less than foam The 55% of quality, water content is less than the 25% of foam gross mass.Outer row's metal ion in solution concentration is not less than 4.2mg/kg。

Embodiment 11:

A kind of separation method rich in carbonate heavy oil field, step is as follows:

As in figure 2 it is shown, Indonesia's oil-sand (carbonate content 56%, the maximum particle diameter pulverized through pulverizer A 0.5cm) with the speed of 5kg/min send in mixing-reactor B with the sulphuric acid that concentration is 5 mol/L and hydrogen Fluoric acid is that 1:5 (mass ratio) is sufficiently mixed at 15 DEG C according to solid-liquid ratio；Serosity after ultrasonic reaction is continuous Output to flotation cell C, carry out flotation.Solution in the middle of flotation cell C loops back reaction with 22kg/min In device.

The extraction rate reached 99.5% of gained asphalt foam, in foam, solid sand grains and the clay of residual are total less than foam The 45% of quality, water content is less than the 32% of foam gross mass.Outer row's metal ion in solution concentration is not less than 7.5g/kg。

A kind of method separated rich in carbonate heavy oil field that the present invention proposes, is entered by preferred embodiment Having gone description, person skilled substantially can be to described herein in without departing from present invention, spirit and scope Structure and technical method is modified or suitably changes and combines, realize the technology of the present invention.Need especially to refer to Go out, all similar replacements and change apparent to those skilled in the art, Ta Mendou It is deemed to be included in present invention spirit, scope and content.

Claims (9)

1. the separation method rich in carbonate heavy oil field, it is characterised in that: heavy oil field and acid solution Mix in mixing channel and react, obtaining the foams mix containing mink cell focus, mineral grain, bubble and water Thing, aqueous solution and solid sediment.

Separation method rich in carbonate heavy oil field the most according to claim 1, it is characterised in that: Handled heavy oil field is the heavy oil field rich in carbonate mine material, as oil-sand, shale oil, landing oil, Greasy filth etc..

Separation method rich in carbonate heavy oil field the most according to claim 2, it is characterised in that: Described carbonate content exceedes the 10% of raw ore mineral content.

Separation method rich in carbonate heavy oil field the most according to claim 1, it is characterised in that: Described heavy oil field is direct material or within pulverizer is crushed to particle diameter 10 centimetres.

Separation method rich in carbonate heavy oil field the most according to claim 1, it is characterised in that: Described with heavy oil field hybrid reaction acid solution be binary or the organic acid of ternary or a kind of acid of mineral acid or The mixed liquor of several acid of person, and acid solution pH value is less than 1.

Separation method rich in carbonate heavy oil field the most according to claim 1, it is characterised in that: Described hybrid reaction temperature is 5～95 DEG C；Within the hybrid reaction time is 2 hours；Hybrid mode for stirring, Ultrasonic, microwave etc..

Separation method rich in carbonate heavy oil field the most according to claim 1, it is characterised in that: The solution that reaction is obtained is the aqueous solution rich in metal ions such as ferrum, calcium, magnesium, aluminum.

Separation method rich in carbonate heavy oil field the most according to claim 1, it is characterised in that: The solid sediment that reaction is obtained is the set containing mineral such as polynary hydrochlorate, silicate and clays.

9. the separation method rich in carbonate heavy oil field, it is characterised in that: step is as follows:

The richest carbonato size-reduced machine of heavy oil field forms less granule after pulverizing, material conveyor send Hybrid reaction is carried out with acid solution to mixing reactor；

The most reacted liquid-solid mixed serum is delivered to flotation cell and carries out flotation layering；The direct extraction of gaseous product, The mink cell focus foam on upper strata is discharged by upper outlet, middle saline solution part circulation, and outside another part, row processes, The residue mineral discharge of bottom processes, and residue mineral includes part calcium precipitation and the undissolved grains of sand, surplus Remaining acid solution is circulated recycling.