CN101735789A - Foam compound oil displacement agent and preparation method thereof - Google Patents
Foam compound oil displacement agent and preparation method thereof Download PDFInfo
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- CN101735789A CN101735789A CN 200910242382 CN200910242382A CN101735789A CN 101735789 A CN101735789 A CN 101735789A CN 200910242382 CN200910242382 CN 200910242382 CN 200910242382 A CN200910242382 A CN 200910242382A CN 101735789 A CN101735789 A CN 101735789A
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- oil displacement
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Abstract
The invention provides a foam compound oil displacement agent, comprising the following components by weight percent: agent A containing 50-70% of urea, 10-30% of ammonium chloride and 8-25% of acid producing substance, agent B containing 30-60% of nitrite, 8-35% of sodium dichloroisocyanurate, 10-20% of surfactant and 10-20% of polymer. The foam compound oil displacement agent provided by the invention enters into stratum or rock shaft, gas is produced by chemical reaction under stratum condition, surfactant and polymer in oil displacement agent are coordinated, and massive foam is formed on the stratum, the generated foam is stable and evenly distributed, the gas produced by self reaction of solution instead of external gas is utilized to form foam, thus simplifying construction process and device.
Description
Technical field
The present invention relates to the tertiary oil production in oil field technology, be specifically related to a kind of foam compound oil displacement agent.
Background technology
Along with the most of oil field of China enters high water-cut development period, tertiary oil recovery technology grows up gradually.Tertiary oil recovery contrast primary oil recovery, secondary oil recovery.At the oil production initial stage, just utilize the natural energy recover petroleum on stratum to be primary oil recovery, recovery ratio only is about 10%; Method by coming recover petroleum to stratum water filling, gas injection is a secondary oil recovery, and recovery ratio generally also can only reach about 25% to 40%; Tertiary oil recovery then is to utilize means such as physics, chemistry and biology, continue the residual petroleum of recovery of subterranean, with regard to the present present situation of China, utilizing chemical means to recover the oil is that chemical flooding remains the main developing direction that oil recovery is improved in China oil field, and wherein foam flooding more and more is subjected to people's attention.
Foam flooding is to utilize the foaminess of tensio-active agent to be made into the method that oil-displacing agent recovers the oil.Foam compound oil displacement agent is the novel displacement system of chemistry and physical method coexistence, and foam viscosity height can improve mobility ratio, increases the high permeability formation resistance to flow, the effect of performance low-permeability layer; Foam blocking profile control ability is strong, has to meet the characteristic that the stable chance oil of water is vanished, thereby has increased the selectivity of shutoff, the stifled oil of water blockoff; Foaming agent can reduce oil water interfacial tension as good promoting agent, improves displacement efficiency; Improve the dispersive ability of oil droplet, improve the flowability of crude oil, therefore use foam compound oil displacement agent can improve oil recovery.
Foam great majority in the foam compound oil displacement agent of using on the oil field at present are formulated by gas and solution on the ground, or make the shaft bottom hydrops become foam by means of the stirring of downhole gas and the tensio-active agent of adding, the foam of Sheng Chenging is stable inadequately like this, and it is even inadequately to distribute in the down-hole.
Summary of the invention
The problem that the present invention solves is to provide a kind of foam compound oil displacement agent, can enter to produce gas by chemical reaction behind the stratum under reservoir condition and form aerated fluid, and the foam stabilization of generation is evenly distributed in the down-hole.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of foam compound oil displacement agent comprises: A agent and B agent;
The weight percent composition that described A agent comprises is:
Urea: 50%～70%
Ammonium chloride: 10%～30%
Acidoid: 8%～25%;
The weight percent composition that described B agent comprises is:
Nitrite: 30%～60%
Dichloroisocyanuric acid sodium: 8%～35%
Tensio-active agent: 10%～20%
Polymkeric substance: 10%～20%.
As preferably, the weight percent of acidoid is 10%～20% in the described A agent.
As preferably, the weight percent of dichloroisocyanuric acid sodium is 10%～30% in the described B agent.
As preferably, described acidoid is for producing the hydrochloric acid material or producing in the organic acidic material one or both.
As preferably, described product hydrochloric acid material is one or more in formaldehyde, Acetyl Chloride 98Min., the trichlorotoluene zotrichloride.
As preferably, described product organic acidic material is the ester class.
As preferably, described tensio-active agent is one or more in heavy alkylbenzene sulfonate, sulfonated petro-leum, a-alkene sulfonate, dialkyl group phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, the ether alcohol sulfate.
As preferably, described polymkeric substance is one or more in polyacrylamide, partially hydrolyzed polyacrylamide, carboxymethyl cellulose, the xanthan gum.
As preferably, the urea in the described A agent and the mol ratio of the nitrite in the B agent are 1: 2～1: 3.
The preparation method of described foam compound oil displacement agent is characterized in that, comprising:
A) urea in the A agent, ammonium chloride, spontaneous acid system are mixed in proportion;
B) nitrite in the B agent, two sodium isocyanurates, tensio-active agent and polymkeric substance are mixed in proportion;
Described A agent and B agent store respectively.
Foam compound oil displacement agent provided by the invention is when entering stratum or pit shaft, under formation condition, produce gas by chemical reaction, cooperate tensio-active agent and polymkeric substance in the oil-displacing agent, form a large amount of foams on the stratum, the foam stabilization that generates and being evenly distributed, because not by external gas, but the gas that utilizes the solution id reaction to produce forms foam, thereby has also simplified construction process and equipment.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Foam compound oil displacement agent provided by the invention is made up of A agent and B agent.The weight percent composition that the A agent comprises is a urea 50%～70%, ammonium chloride 10%～30%, and acidoid 8%～25% is preferably 10%～20%.The weight percent composition that the B agent comprises is a nitrite 30%～60%, and dichloroisocyanuric acid sodium 8%～35% is preferably 10%～30%, tensio-active agent 10%～20%, polymkeric substance 10%～20%.
In oil displacement process, mainly be urea in the A agent and the nitrite in the B agent generation gas that reacts, the mol ratio of preferred urea of the present invention and nitrite is 1: 2～1: 3, and therefore, A agent and B agent are just prepared according to the mol ratio of urea and nitrite in use.
In the A agent, acidoid here refers in depositing at ordinary times and does not react, and reacting under the condition on the stratum after injecting the stratum or after running into water to generate the material of acid.
Acidoid is one or both in product hydrochloric acid material or the product organic acidic material.Produce the hydrochloric acid material and be behind the injection stratum reacting under the formation condition or after running into water and can generate the material of hydrochloric acid, the present invention is preferably one or more in formaldehyde, Acetyl Chloride 98Min., the trichlorotoluene zotrichloride.
Formaldehyde under the condition of high voltage on stratum with the A agent in ammonium chloride reaction generate HCl, reaction equation is: 6HCHO+4NH
4Cl → C
6H
12N
4+ 4HCl+6H
2O;
Hydrolysis reaction takes place after meeting water in Acetyl Chloride 98Min., generates HCl, and reaction equation is: CH
3COCl+H
2O → CH
3COOH+HCl;
Hydrolysis reaction takes place after meeting water in trichlorotoluene zotrichloride, generates HCl, and reaction equation is: C
7H
5Cl
3+ H
2O → C
7H
6O
2
Produce organic acidic material and be behind the injection stratum reacting under the formation condition or after running into water and can generate the organic acid material, the present invention is preferably the ester class, meet water generation hydrolysis reaction as ethyl acetate under the high-temperature and high-pressure conditions on stratum, generate acetate, reaction equation is: C
4H
8O
2+ H
2O → C
2H
4O
2+ C
2H
6O.
In the B agent, preferred Sodium Nitrite of nitrite or potassium nitrite, be mainly used to the A agent in urea react, generate CO
2And N
2Gas.
Surchlor GR 60 can be met water generation hydrolysis reaction after injecting the stratum under formation condition, generate hypochlorous acid, and reaction equation is: C
3Cl
2N
3O
3Na+3H
2O → 2HClO+C
3H
3N
3O
3+ NaOH.
Tensio-active agent is preferably one or more in heavy alkylbenzene sulfonate, sulfonated petro-leum, a-alkene sulfonate, dialkyl group phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, the ether alcohol sulfate.The main effect of tensio-active agent is to bubble, and reduces oil water interfacial tension simultaneously, reduces the corrosion of oil well and equipment, and emulsification reduces viscosity of crude.
Polymkeric substance is preferably one or more in polyacrylamide, partially hydrolyzed polyacrylamide, carboxymethyl cellulose, the xanthan gum.The main effect of polymkeric substance is a stable foam, the diffusion that the grid structure of polymkeric substance can stop fine foam to be, the speed of control reaction simultaneously, the mobility of increase oil-displacing agent.
The action principle of foam compound oil displacement agent provided by the invention is:
After being injected into the stratum after A agent and B agent mix, under certain formation condition, acidoid reacts and generates hydrochloric acid or organic acid, the dichloroisocyanuric acid sodium reaction generates hypochlorous acid, hydrochloric acid that generates or organic acid constitute complex acid catalyst with hypochlorous acid, can cause urea and the nitrite a large amount of CO of generation that reacts
2And N
2, under the effect of tensio-active agent and polymkeric substance, form a large amount of stable foams and discharge heat.The concrete urea and the reaction equation of Sodium Nitrite are: CO (NH
2)
2+ NH
4 ++ 3NO
2 -+ 2H
+→ 3N
2↑+CO
2↑+5H
2O+Q (heat).
A large amount of gases that reaction produces can increase the oil reservoir energy, form stable solution-air foaming system, can produce very big addedresistance for injection water afterwards, form barrier, stop up most permeable zone, break original underground fluid balance, form new underground fluid balance, increase swept volume, effectively improve intake profile, be communicated with formation pore, displace interpore crude oil, induce the non-crude oil of employing the district to flow out, improve the crude oil recovery ratio.Foam can also be removed pollution, dispersion, dissolved bitumen matter, the colloid of oil deposit deep part, removes organic obstruction, reduces water injection pressure, and suppresses the clay swelling migration.The hotwork of gas and reaction generation is used for the viscosity that oil phase can reduce crude oil, CO in addition
2Gas improves the effect of oil reservoir discharge opeing ability, washing oil, N in addition
2Gas can react with the amino acid in the crude oil, generates performance surface of good promoting agent, makes rock surface be water-wet, reduces oil flow resistance.
The preparation method of foam compound oil displacement agent of the present invention is:
A) urea in the A agent, ammonium chloride, spontaneous acid system are mixed in proportion, stir, packing and storing;
B) nitrite in the B agent, two sodium isocyanurates, tensio-active agent and polymkeric substance are mixed in proportion, stir packing and storing.
A agent and B agent will store respectively, can not stack mutually, prevent that urea and nitrite from reacting, and need moistureproof and waterproof, prevent acidoid chance water generation hydrolysis wherein, make oil-displacing agent rotten.When using at the scene, A agent and B agent were preferably prepared according to the mol ratio of urea and nitrite in 1: 2～1: 3.
Embodiment 1:
A agent: the ammonium chloride 20% of urea 70%, the Shanghai living flower bud chemical industry company limited of chemical reagent company limited of Tianjin Jin Hui the Pacific-Asian, the dichloroisocyanuric acid sodium 10% of Shandong sunlight chemical industry company limited.
B agent: the partially hydrolyzed polyacrylamide 15% of the formaldehyde 10% of the Sodium Nitrite 60% of the photochemical factory in Shandong, Shandong, Harbin Di Kelun chemical industry company limited, the heavy alkylbenzene sulfonic acid sodium 15% of Xiongguan Science ﹠ Tech., Ltd., Tianjin, the good chemical industry in source, Shanghai company limited.
Embodiment 2:
A agent: the Acetyl Chloride 98Min. 20% of the ammonium chloride 15% of urea 65%, the Shanghai living flower bud chemical industry company limited of chemical reagent company limited of Tianjin Jin Hui the Pacific-Asian, profit source, Changzhou chemical industry company limited.
The B agent: Nanjing is contained potassium nitrite 50%, the dichloroisocyanuric acid sodium 15% of Shandong sunlight chemical industry company limited, the Guangzhou of Khanh Hoa chemical industry company limited and is contained and reach the polyoxyethylenated alcohol sodium sulfate 20% of chemical industry company limited, the carboxymethyl cellulose 15% of the wide petrochemical industry of North China oil company limited.
Embodiment 3:
A agent: the ammonium chloride 15% of urea 60%, the Shanghai living flower bud chemical industry company limited of chemical reagent company limited of Tianjin Jin Hui the Pacific-Asian, the trichlorotoluene zotrichloride 25% of Zhejiang Dongyang Xinghua Chemical Co., Ltd..
The B agent: the a-alkene sulfonic acid sodium 15% of the neat safe chemical industry in dichloroisocyanuric acid sodium 25%, the Guangzhou of the Sodium Nitrite 40% of the photochemical factory in Shandong, Shandong, Shandong sunlight chemical industry company limited company limited, Zibo are along the xanthan gum 20% that reaches bio tech ltd.
Embodiment 4:
Foam compound oil displacement agent weight percent composition provided by the invention is:
A agent: the ammonium chloride 30% of urea 50%, the Shanghai living flower bud chemical industry company limited of chemical reagent company limited of Tianjin Jin Hui the Pacific-Asian, the ethyl acetate 20% of Nantong Acetic Acid Co., Ltd.
B agent: the sulfonated petro-leum 20% of the Feng Huagong company limited of the potassium nitrite 30% of Nanjing Sheng Khanh Hoa chemical industry company limited, the dichloroisocyanuric acid sodium 30% of Shandong sunlight chemical industry company limited, Shanghai ancient cooking vessel, the polyacrylamide 20% of Beijing Hengju Chemical Group Co., Ltd.
During experiment, use artificial heterogeneous core to simulate, be of a size of 4.5cm * 4.5cm * 30cm, vertically divide three layers, each layer thickness is 1.5cm, and each layer rate of permeation is respectively 500md, 1500md and 4000md from top to bottom.At first carry out water drive by water filling port injection experiments water, water drive is injected foam compound oil displacement agent provided by the invention after artificial homogeneous rock core comprehensive water cut 98%, injects multiple and all gets 0.3PV, and experimental result sees Table 1:
The oil displacement experiment result of table 1 foam compound oil displacement agent
| Oil-displacing agent | Waterflood recovery efficiency factor (%) | Improve recovery ratio (%) | Overall recovery factor (%) |
| Embodiment 1 | ??29.77 | ??14.53 | ??44.30 |
| Embodiment 2 | ??29.77 | ??13.25 | ??43.02 |
| Embodiment 3 | ??29.77 | ??14.31 | ??44.08 |
| Embodiment 4 | ??29.77 | ??12.71 | ??42.48 |
Foam compound oil displacement agent provided by the invention is after entering stratum or pit shaft, under formation condition, just produce gas and form a large amount of foams by chemical reaction, foam stabilization and being evenly distributed, and as can be seen by above experimental data, the recovery ratio of this foam compound oil displacement agent is higher, can improve about 10%～15% than water drive.
More than the preparation method of foam compound oil displacement agent provided by the present invention and this foam compound oil displacement agent is described in detail.Used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. a foam compound oil displacement agent is characterized in that, comprising: A agent and B agent;
The weight percent composition that described A agent comprises is:
Urea: 50%～70%
Ammonium chloride: 10%～30%
Acidoid: 8%～25%;
The weight percent composition that described B agent comprises is:
Nitrite: 30%～60%
Dichloroisocyanuric acid sodium: 8%～35%
Tensio-active agent: 10%～20%
Polymkeric substance: 10%～20%.
2. foam compound oil displacement agent according to claim 1 is characterized in that, the weight percent of acidoid is 10%～20% in the described A agent.
3. foam compound oil displacement agent according to claim 1 is characterized in that, the weight percent of dichloroisocyanuric acid sodium is 10%～30% in the described B agent.
4. according to each described foam compound oil displacement agent in the claim 1 to 3, it is characterized in that described acidoid is one or both in product hydrochloric acid material or the product organic acidic material.
5. foam compound oil displacement agent according to claim 4 is characterized in that, described product hydrochloric acid material is one or more in formaldehyde, Acetyl Chloride 98Min., the trichlorotoluene zotrichloride.
6. foam compound oil displacement agent according to claim 4 is characterized in that, described product organic acidic material is the ester class.
7. according to each described foam compound oil displacement agent in the claim 1 to 3, it is characterized in that described tensio-active agent is one or more in heavy alkylbenzene sulfonate, sulfonated petro-leum, a-alkene sulfonate, dialkyl group phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, the ether alcohol sulfate.
8. according to each described foam compound oil displacement agent in the claim 1 to 3, it is characterized in that described polymkeric substance is one or more in polyacrylamide, partially hydrolyzed polyacrylamide, carboxymethyl cellulose, the xanthan gum.
9. according to each described foam compound oil displacement agent in the claim 1 to 3, it is characterized in that the urea in the described A agent and the mol ratio of the nitrite in the B agent are 1: 2～1: 3.
10. the preparation method of each described foam compound oil displacement agent in the claim 1 to 9 is characterized in that, comprising:
A) urea in the A agent, ammonium chloride, spontaneous acid system are mixed in proportion;
B) nitrite in the B agent, two sodium isocyanurates, tensio-active agent and polymkeric substance are mixed in proportion;
Described A agent and B agent store respectively.
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