CN103011337A - Polymer flooding produced liquid polymer retaining comprehensive treatment agent and application method - Google Patents
Polymer flooding produced liquid polymer retaining comprehensive treatment agent and application method Download PDFInfo
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- CN103011337A CN103011337A CN2012104236052A CN201210423605A CN103011337A CN 103011337 A CN103011337 A CN 103011337A CN 2012104236052 A CN2012104236052 A CN 2012104236052A CN 201210423605 A CN201210423605 A CN 201210423605A CN 103011337 A CN103011337 A CN 103011337A
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Abstract
The invention discloses a polymer flooding produced liquid polymer retaining comprehensive treatment agent which is formed by compounding a demulsifying agent and a water purifying agent. By taking phenol-formaldehyde resin as an initiator and an alkali compound as a catalyst, the phenol-formaldehyde resin firstly reacts with propylene oxide to obtain a propoxylation polyether compound which conducts an addition reaction with ethylene oxide under the effect of an alkali catalyst, and the formed intermediate sequentially reacts with propylene oxide and ethylene oxide and finally conducts a polymerization reaction with propylene oxide to synthesize the demulsifying agent. The water purifying agent is a polyoxyethylene polyoxypropylene polymer, wherein by taking propylene glycol as an initiator and an alkali compound as a catalyst, the propylene glycol firstly reacts with propylene oxide to obtain a propoxylation polyether compound which reacts with propylene oxide under the effect of the alkali catalyst to synthesize a polyether compound; the polyether compound reacts with ethylene oxide under the effect of the alkali catalyst to generate a polyoxyethylene polyoxypropylene block copolymer; and by taking maleic anhydride as a chain extender and p-toluenesulfonic acid as a catalyst, chain extension modification is performed to obtain the water purifying agent.
Description
Technical field
The present invention relates to a kind of Produced in Polymer Flooding liquid polymkeric substance and keep comprehensive treatment agent and application method.
Background technology
In the eighties mid-term in last century, the polymer displacement of reservoir oil tech of showing one's talent from chemical flooding progresses into field test and practical stage, demonstrates the applications well prospect.Applying of polymer displacement of reservoir oil tech effectively raises oil recovery factor, and oil increasing effect is obvious, also produced accordingly a large amount of polymer-bearing waste-waters.Polymkeric substance is underground through injecting, and along with the oil reservoir migration, gets back on the ground with Produced Liquid, has increased emulsion droplet interfacial electric double layer negative charge density on the one hand, has strengthened electrostatic repulsion between drop; Bulk viscosity raises on the other hand, has strengthened dispersant liquid drop and has mutually collided poly-difficulty also.Thereby increased Produced Liquid emulsion dispersion stability of system, intractability is large, causes the adaptability variation of conventional processing agent and related process.
At present, the method for oilfield treatments polymer-bearing waste-water is that the water treatment agent that adds based on flocculation mechanism cooperates corresponding processing unit to process.These water conditioners are mainly flocculation agent and cationic polymer medicament.Its mechanism all is by electrical neutralization, changes the molecularity of polymkeric substance in the water, forms and carries crude oil and a large amount of flco of suspended substance, to reach the purpose of purification.But the sinking in system of this flco can form and contain poly-greasy filth, has reduced the useful volume of slurry tank, becomes simultaneously the hotbed of bacteria breed, has aggravated equipment corrosion.Contain poly-greasy filth and cause low-pressure adjusting water pipeline, high pressure water injection pipeline and filter stoppage in the deposition of waterflood system, reduced the defeated efficient of collection, increased corrosion speed, brought water pollution once again, affect the normal production in oil field.
Summary of the invention
The object of the invention provides a kind of polymer flooding polymkeric substance and keeps comprehensive treatment agent and application method, the polymkeric substance reservation comprehensive treatment agent that purifies by in containing poly-Produced Liquid, adding this profit two-phase, polymkeric substance in the sewage can be retained in the water, avoid containing the generation of poly-greasy filth.
Polymkeric substance keeps composite the forming of water purification agent that comprehensive treatment agent is synthesized by synthetic emulsion splitter and four-step reaction through the reaction of five steps, emulsion splitter is take resol as initiator, basic cpd is catalyzer, obtain the propoxylation polyether compound with propylene oxide reaction first, carry out addition reaction with oxyethane under the alkaline catalysts effect again, the intermediate of formation is priority and propylene oxide again, and oxyethane reacts according to this, carry out polyreaction with propylene oxide more at last, synthetic emulsion splitter; Water purification agent is POLOXAMERS, and take propylene glycol as initiator, basic cpd is catalyzer, obtains the propoxylation polyether compound with propylene oxide reaction first, reacts the synthesizing polyether compound under the alkaline catalysts effect with propylene oxide again.And with it under the alkaline catalysts effect, generate polyoxyethylene polyoxypropylene block copolymer with reacting ethylene oxide.Make chainextender with MALEIC ANHYDRIDE again, take tosic acid as catalyzer, carry out the chain extension modification and obtain water scavengine agent.
Emulsion splitter is synthetic: basic cpd is potassium hydroxide, and in the first step reaction, initiator, basic cpd, propylene oxide mass ratio are 25～40:0.05～0.25:60～140; In the second step reaction, the intermediate of the first step, basic cpd, oxyethane mass ratio are 25～35:0.05～0.25:60～95; In the three-step reaction, the intermediate of second step, basic cpd, propylene oxide mass ratio are 15～40:0.05～0.25:80～140; In the four-step reaction, intermediate, basic cpd, the oxyethane mass ratio in the 3rd step are 25～35:0.05～0.25:70～100; In the reaction of the 5th step, intermediate, basic cpd, the propylene oxide mass ratio in the 4th step are 25～40:0.05～0.3:80～120; Reaction times 3～the 8h in above-mentioned per step, 100～140 ℃ of temperature of reaction, reaction pressure-0.08～0.4MPa.
In the water purification agent building-up reactions, in the first step reaction, initiator, basic cpd, propylene oxide mass ratio are 10～20:0.05～0.25:120～170; In the second step reaction, the intermediate of the first step, basic cpd, propylene oxide mass ratio are 15～25:0.05～0.25:110～160; In the three-step reaction, intermediate, basic cpd, oxyethane mass ratio are 10～25:0.1～0.25:80～140; The temperature of reaction in above-mentioned per step is 80 ℃～180 ℃, reaction times 4～8h, and reaction pressure is-0.08～0.4MPa.In the four-step reaction, in the intermediate polyoxyethylene polyoxypropylene block copolymer chain extension modified-reaction that above-mentioned the 3rd step is produced, initiator, catalyzer, chainextender mass ratio are 50～80:0.05～0.08:40～90; 100 ℃～150 ℃ of temperature of reaction, reaction times 3～5h, reaction pressure is controlled at 0.08～0.1MPa.
Above-mentioned synthetic emulsion splitter molecular weight is 6K～10W; The water purification agent molecular weight is 8k～2W, emulsion splitter and water purification agent is carried out composite, and composite ratio of quality and the number of copies is two kinds of comprehensive treatment agents of 1:1 and 1:5, and concrete code name is GD-D1 and GD-D2.
GD-D1 and GD-D2 at the scene in the sewage chemical feeding quantity of composite rear comprehensive treatment agent be 30～70mg/L, be specifically as follows 30 mg/L or 50 mg/L.
Polymkeric substance keeps the application method of comprehensive treatment agent: GD-D1 type or GD-D2 comprehensive treatment agent are added 30 mg/L or 50 mg/L from individual well well array pipeline, O/W milk sap micro interface in the polymer-bearing waste-water is carried out the target medication, under the effect of GD-D1 or GD-D2, weaken electrostatic double layer, reduce system stability, do not change polymer molecular structure, form " reversible gathering also ".Capture through crude oil, except anhydrating middle oil-containing, utilize simultaneously the intermolecular interaction of water and polymkeric substance, polymkeric substance is retained in the water, avoid generation to contain poly-greasy filth.
The present invention has the following advantages: (1) compound drug only need add at well array and come the liquid place, does not need to repeat to add; (2) emulsion splitter and water purification agent are composite adds, and the oil removing purifying water effect is better than the single-component medicament; (3) polymkeric substance retention rate 〉=95% is retained in polymkeric substance in the sewage, does not produce to contain poly-flco, has avoided containing the generation of poly-greasy filth and ageing oil.
Embodiment
Polymkeric substance keeps composite the forming of water purification agent that comprehensive treatment agent is synthesized by synthetic emulsion splitter and four-step reaction through the reaction of five steps, emulsion splitter is take resol as initiator, basic cpd is catalyzer, obtain the propoxylation polyether compound with propylene oxide reaction first, carry out addition reaction with oxyethane under the alkaline catalysts effect again, the intermediate of formation is priority and propylene oxide again, and oxyethane reacts according to this, carry out polyreaction with propylene oxide more at last, synthetic emulsion splitter; Water purification agent is POLOXAMERS, and take propylene glycol as initiator, basic cpd is catalyzer, obtains the propoxylation polyether compound with propylene oxide reaction first, reacts the synthesizing polyether compound under the alkaline catalysts effect with propylene oxide again.And with it under the alkaline catalysts effect, generate polyoxyethylene polyoxypropylene block copolymer with reacting ethylene oxide.Make chainextender with MALEIC ANHYDRIDE again, take tosic acid as catalyzer, carry out the chain extension modification and obtain water purification agent.
Example 1: get Polymer Flooding of Gudao Oilfield 33-529 single well fluid and carry out the experiment of bottle examination method medicament in the laboratory, comprehensive treatment agent GD-D1, chemical feeding quantity are 50mg/L, and temperature is 50 ℃, shakes sedimentation 4h 200 times.Crude oil water containing is 2% after processing, oil-containing 5633mg/L before the sewage disposal, and oil-containing 82mg/L after processing, oil removal rate reaches 98%.Being 482mg/L before the polymer treatment in the sewage, is 463mg/L after processing, and retention rate has reached 96%.
Example 2:2012 June-October, the integrated processing skid-mounted device of applied chemistry flooding produced liquid has been carried out 4 months test in place at No. two connection in lonely east, this skid-mounted device treatment capacity 150m3/d, coming the liquid ingress to add comprehensive treatment agent GD-D2, chemical feeding quantity 25mg/L water polymer content 254.1mg/L, outer water delivery polymer content 242mg/L after device is processed, retention rate has reached 95.2%, and duration of test does not produce and contains poly-greasy filth, does not cause the obstruction of device.
Claims (6)
1. a polymer flooding polymkeric substance keeps comprehensive treatment agent, by going on foot the synthetic emulsion splitter of reaction and composite the forming of water purification agent that four-step reaction synthesizes through five, emulsion splitter is take resol as initiator, basic cpd is catalyzer, obtain the propoxylation polyether compound with propylene oxide reaction first, under the alkaline catalysts effect, carry out addition reaction with oxyethane again, the intermediate that forms is priority and propylene oxide again, oxyethane reacts according to this, carry out polyreaction with propylene oxide more at last, synthetic emulsion splitter; Water purification agent is POLOXAMERS, and take propylene glycol as initiator, basic cpd is catalyzer, obtains the propoxylation polyether compound with propylene oxide reaction first, reacts the synthesizing polyether compound under the alkaline catalysts effect with propylene oxide again; And with it under the alkaline catalysts effect, generate polyoxyethylene polyoxypropylene block copolymer with reacting ethylene oxide; Make chainextender with MALEIC ANHYDRIDE again, take tosic acid as catalyzer, carry out the chain extension modification and obtain water scavengine agent.
2. polymer flooding polymkeric substance according to claim 1 keeps comprehensive treatment agent, it is characterized in that the breakdown of emulsion reactions steps is: basic cpd is potassium hydroxide, in the first step reaction, initiator, basic cpd, propylene oxide mass ratio are 25～40:0.05～0.25:60～140; In the second step reaction, the intermediate of the first step, basic cpd, oxyethane mass ratio are 25～35:0.05～0.25:60～95; In the three-step reaction, the intermediate of second step, basic cpd, propylene oxide mass ratio are 15～40:0.05～0.25:80～140; In the four-step reaction, intermediate, basic cpd, the oxyethane mass ratio in the 3rd step are 25～35:0.05～0.25:70～100; In the reaction of the 5th step, intermediate, basic cpd, the propylene oxide mass ratio in the 4th step are 25～40:0.05～0.3:80～120; Reaction times 3～the 8h in above-mentioned per step, 100～140 ℃ of temperature of reaction, reaction pressure-0.08～0.4MPa.
3. polymer flooding polymkeric substance according to claim 1 keeps comprehensive treatment agent, it is characterized in that the water purification agent reactions steps is: in the first step reaction, initiator, basic cpd, propylene oxide mass ratio are 10～20:0.05～0.25:120～170; In the second step reaction, the intermediate of the first step, basic cpd, propylene oxide mass ratio are 15～25:0.05～0.25:110～160; In the three-step reaction, intermediate, basic cpd, oxyethane mass ratio are 10～25:0.1～0.25:80～140; The temperature of reaction in above-mentioned per step is 80 ℃～180 ℃, reaction times 4～8h, and reaction pressure is-0.08～0.4MPa; In the four-step reaction, in the intermediate polyoxyethylene polyoxypropylene block copolymer chain extension modified-reaction that above-mentioned the 3rd step is produced, initiator, catalyzer, chainextender mass ratio are 50～80:0.05～0.08:40～90; 100 ℃～150 ℃ of temperature of reaction, reaction times 3～5h, reaction pressure is controlled at 0.08～0.1MPa.
According to claim 1 and 2 or 3 described polymer flooding polymkeric substance keep comprehensive treatment agents, it is characterized in that the emulsion splitter molecular weight is 6K～10W; The water purification agent molecular weight is 8k～2W, emulsion splitter and water purification agent is carried out composite, and composite ratio of quality and the number of copies is two kinds of comprehensive treatment agents of 1:1 and 1:5, and concrete code name is GD-D1 and GD-D2.
According to claim 1 or 4 described polymer flooding polymkeric substance keep comprehensive treatment agents, it is characterized in that GD-D1 and GD-D2 at the scene in the sewage chemical feeding quantity of composite rear comprehensive treatment agent be 30～70mg/L, be specifically as follows 30 mg/L or 50 mg/L.
6. a polymer flooding polymkeric substance keeps the application method of comprehensive treatment agent, refer to the claims 1 and 5 described comprehensive treatment agents, GD-D1 type or GD-D2 comprehensive treatment agent are added 30 mg/L or 50 mg/L from individual well well array pipeline, O/W milk sap micro interface in the polymer-bearing waste-water is carried out the target medication, under the effect of GD-D1 or GD-D2, weaken electrostatic double layer, reduce system stability, do not change polymer molecular structure, form " reversible gathering also "; Capture through crude oil, except anhydrating middle oil-containing, utilize simultaneously the intermolecular interaction of water and polymkeric substance, polymkeric substance is retained in the water, avoid generation to contain poly-greasy filth.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396828A (en) * | 2013-07-26 | 2013-11-20 | 金浦新材料股份有限公司 | Polyether crude oil demulsifier using straight chain alkyl phenolic resin as initiator and preparation method and application thereof |
| CN104650336A (en) * | 2015-02-11 | 2015-05-27 | 胜利油田胜利化工有限责任公司 | Preparation method of novel organic amine demulsifier |
| CN105093862A (en) * | 2015-09-25 | 2015-11-25 | 富士胶片电子材料（苏州）有限公司 | Surface active agent and developing solution used for color filter negative photoresist |
| CN105347453A (en) * | 2015-11-12 | 2016-02-24 | 威海翔宇环保科技股份有限公司 | Processing technology of mixed liquid containing various plant oils and used for carpet industry |
| CN106832254A (en) * | 2017-02-22 | 2017-06-13 | 济南惠信实业有限公司 | The preparation method of desalination type demulsifier |
| CN107601619A (en) * | 2017-10-25 | 2018-01-19 | 成都凯米拉科技有限公司 | A kind of preparation technology of water process demulsifier |
| CN108585156A (en) * | 2018-05-15 | 2018-09-28 | 天津正达科技有限责任公司 | A kind of flocculant and preparation method thereof removing COD in coal gasification phenol wastewater |
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| CN1537924A (en) * | 2003-10-22 | 2004-10-20 | 山东大学 | Low-temperature quick deemulsifying agent for water-containing wax-containing erude oil and its preparation method |
| CN1772844A (en) * | 2005-11-15 | 2006-05-17 | 中国石化胜利油田有限公司孤东采油厂 | Binary re-compound oil soluble demulsifier |
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| CN1537924A (en) * | 2003-10-22 | 2004-10-20 | 山东大学 | Low-temperature quick deemulsifying agent for water-containing wax-containing erude oil and its preparation method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396828A (en) * | 2013-07-26 | 2013-11-20 | 金浦新材料股份有限公司 | Polyether crude oil demulsifier using straight chain alkyl phenolic resin as initiator and preparation method and application thereof |
| CN104650336A (en) * | 2015-02-11 | 2015-05-27 | 胜利油田胜利化工有限责任公司 | Preparation method of novel organic amine demulsifier |
| CN105093862A (en) * | 2015-09-25 | 2015-11-25 | 富士胶片电子材料（苏州）有限公司 | Surface active agent and developing solution used for color filter negative photoresist |
| CN105347453A (en) * | 2015-11-12 | 2016-02-24 | 威海翔宇环保科技股份有限公司 | Processing technology of mixed liquid containing various plant oils and used for carpet industry |
| CN106832254A (en) * | 2017-02-22 | 2017-06-13 | 济南惠信实业有限公司 | The preparation method of desalination type demulsifier |
| CN106832254B (en) * | 2017-02-22 | 2019-01-04 | 济南惠信实业有限公司 | The preparation method of desalination type demulsifier |
| CN107601619A (en) * | 2017-10-25 | 2018-01-19 | 成都凯米拉科技有限公司 | A kind of preparation technology of water process demulsifier |
| CN108585156A (en) * | 2018-05-15 | 2018-09-28 | 天津正达科技有限责任公司 | A kind of flocculant and preparation method thereof removing COD in coal gasification phenol wastewater |
| CN108585156B (en) * | 2018-05-15 | 2021-05-04 | 天津正达科技有限责任公司 | Flocculant for removing COD (chemical oxygen demand) in coal gasification phenol-containing wastewater and preparation method thereof |
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Application publication date: 20130403 |