CN100513526C - Dehydration demulsifier for produced liquid of polymer flooding crude oil - Google Patents
Dehydration demulsifier for produced liquid of polymer flooding crude oil Download PDFInfo
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- CN100513526C CN100513526C CNB200610064907XA CN200610064907A CN100513526C CN 100513526 C CN100513526 C CN 100513526C CN B200610064907X A CNB200610064907X A CN B200610064907XA CN 200610064907 A CN200610064907 A CN 200610064907A CN 100513526 C CN100513526 C CN 100513526C
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- 239000010779 crude oil Substances 0.000 title claims abstract description 42
- 230000018044 dehydration Effects 0.000 title claims abstract description 16
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 16
- 239000007788 liquid Substances 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 210000003298 dental enamel Anatomy 0.000 claims abstract description 4
- 239000013543 active substance Substances 0.000 claims description 60
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 24
- 238000010792 warming Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 230000001846 repelling effect Effects 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- HMRWGKIZOBXNRB-UHFFFAOYSA-N octane-1-sulfonyl fluoride Chemical compound CCCCCCCCS(F)(=O)=O HMRWGKIZOBXNRB-UHFFFAOYSA-N 0.000 claims description 5
- -1 phenol amine Chemical class 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 12
- 239000010865 sewage Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 13
- 238000000605 extraction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
A demulsifier for dewatering polymer flooding crude oil and a preparation method thereof. The method is characterized in that: firstly, respectively preparing three surfactants, then placing the three surfactants in an enamel mixing kettle, stirring, heating, dropwise adding methanol and water, and cooling to obtain the demulsifier for dewatering the polymer flooding crude oil. The demulsifying and dehydrating effects of the demulsifier are superior to those of the conventional demulsifier. In the dehydration of crude oil, the dosage of a dehydration demulsifier of a polymer flooding crude oil production liquid is small, the water content of the dehydrated crude oil is less than 0.2 percent, and the oil content of sewage is less than 50 mg/l. The water content of the crude oil after dehydration meets the requirement; the oil content in the sewage is reduced from above 5500mg/l to below 50 mg/l.
Description
Affiliated technical field
The present invention relates to a kind of poly-repelling crude oil demulsifying agent for dehydration, gather the preparation method of repelling crude oil with emulsion splitter.
Background technology
Reach outer defeated branded oil standard after solving dehydrating of crude oil, it is up to standard to take off back sewage, reduces the breaking emulsion and dewatering cost of crude oil, and the technician has developed numerous species type emulsion splitter at the site technology problem.Solved many crude oil demulsification dehydration problems, but the technical problem that has is out in the cold.Such as, the extraction liquid that contains polymkeric substance is behind breaking emulsion and dewatering, and how oleaginousness height in the sewage should solve.
For improving the latter period of oilfield development reservoir coverage, can obtain some workable reserve, improve oil recovery factor.The production technique personnel have carried out as polymer flooding modes such as weak gel profile drive some oil fields.Caused like this in the extraction liquid and contained polymkeric substance, cause using conventional emulsion splitter to handle the extraction fluid dewatering after, moisture height in the isolated crude oil contains innage in the sewage.When conventional emulsion splitter dosage reaches 500mg/l, can make that dehydrating of crude oil is moisture to reach 1.0% corrected oil standard, but oil content of wastewater is still up to more than the 5500mg/l.Do not reach the oily(waste)water of emission standard, need to handle again just can reach emission standard.Like this, not only dehydrating of crude oil processing costs height simultaneously, has caused very big difficulty to sewage disposal.
Summary of the invention
The objective of the invention is: a kind of produced fluid dewatering demulsifier for accumulating and repelling crude oil and preparation method thereof is provided, makes a kind of poly-repelling crude oil emulsion splitter, realize that poly-repelling crude oil dehydration water content is less than 0.5% branded oil standard; And oleaginousness reaches emission standard simultaneously in the sewage.Overcome existing emulsion splitter and can only realize the moisture 1.0% corrected oil standard that reaches of dehydrating of crude oil, oil content of wastewater does not reach the problem of emission standard.
The technical scheme that the present invention is taked for its technical problem of solution is:
Produced fluid dewatering demulsifier for accumulating and repelling crude oil, formulation weight per-cent is: A tensio-active agent, 10～45%; The B tensio-active agent, 5～50%; The C tensio-active agent, 10～45%; Methyl alcohol, 20～45%; Water, 10～25%.Wherein:
The raw material weight per-cent of A tensio-active agent is: PEA, 15～59%; Potassium hydroxide, 0.1～0.25%; Propylene oxide, 40～84%.A tensio-active agent raw material all components and be 100%.Wherein: PEA is by full-fluorine octyl sulfuryl fluoride, 10-65%; Oxyethane, 35-90% preparation.
The raw material weight per-cent of B tensio-active agent is: PEB, 20～59%; Potassium hydroxide, 0.1～0.25%; Propylene oxide, 40～79%.B tensio-active agent raw material all components and be 100%.Wherein: PEB is by phenolic resin, 10-70%; Oxyethane, 30-90% preparation.
The raw material weight per-cent of C tensio-active agent is: PEC, 15～64%; Potassium hydroxide, 0.1～0.25%; Propylene oxide, 35～84%.C tensio-active agent raw material all components and be 100%.Wherein: PEC is by phenol amine resin, 14-68%; Oxyethane, 32-86% preparation.
The preparation method of produced fluid dewatering demulsifier for accumulating and repelling crude oil of the present invention be divided into following four the step finish:
One, the preparation of A tensio-active agent
At first, with the weight percent of preparation intermediate PEA is that 10%-65% full-fluorine octyl sulfuryl fluoride is that initiator places stainless steel cauldron, start stirring, be warming up to 120 ± 5 ℃, find time, fill nitrogen, slowly drip weight ratio and be 35%-90% oxyethane.Reaction pressure is controlled at 0.2～0.5MPa, dropwises, and after question response still internal pressure returned zero, cooling discharge obtained intermediate PEA.
With the weight ratio of preparation A tensio-active agent is that 15%～59% intermediate PEA and weight ratio are that 0.1%～0.25% potassium hydroxide places stainless steel cauldron, start stirring, be warming up to 130 ± 5 ℃, find time, fill nitrogen, slowly drip weight ratio and be 40%～84% propylene oxide.Reaction pressure is controlled at 0.2～0.5MPa, dropwises, and after question response still internal pressure returned zero, cooling discharge obtained the A tensio-active agent.A tensio-active agent raw material all components and be 100%.
Two, the preparation of B tensio-active agent
At first, be that 10-70% phenolic resin initiator places stainless steel cauldron with the weight ratio of preparation intermediate PEB, start stirring, be warming up to 125 ± 5 ℃, find time, fill nitrogen, slowly drip weight ratio and be 30%～90% oxyethane.Reaction pressure is controlled at 0.2～0.5MPa, dropwises, and after question response still internal pressure returned zero, cooling discharge obtained intermediate PEB.
With the weight ratio of preparation B tensio-active agent is that 20%～59% intermediate PEB and weight ratio are that 0.1～0.25% potassium hydroxide places stainless steel cauldron, start stirring, be warming up to 135 ± 5 ℃, find time, fill nitrogen, slowly drip weight ratio and be 40%～79% propylene oxide.Reaction pressure is controlled at 0.2～0.5MPa, dropwises, and after question response still internal pressure returned zero, cooling discharge obtained the B tensio-active agent.B tensio-active agent raw material all components and be 100%.
Three, the preparation of C tensio-active agent
At first, with the weight ratio of preparation intermediate PEC is that 14-68% phenol amine resin initiator places stainless steel cauldron, start stirring, be warming up to 120 ± 5 ℃, find time, fill nitrogen, slowly the dropping weight ratio is 32%～86% oxyethane, and reaction pressure is controlled at 0.2～0.5MPa, dropwises, after question response still internal pressure returned zero, cooling discharge obtained intermediate PEC.
With the weight ratio of preparation C tensio-active agent is that 15%～64% intermediate PEC and weight ratio are that 0.1～0.25% potassium hydroxide places stainless steel cauldron, start stirring, be warming up to 135 ± 5 ℃, find time, fill nitrogen, slowly drip weight ratio and be 35%～84% propylene oxide.Reaction pressure is controlled at 0.2～0.5MPa, dropwises, and after question response still internal pressure returned zero, cooling discharge obtained the C tensio-active agent.C tensio-active agent raw material all components and be 100%.
Four, the preparation of poly-repelling crude oil demulsifying agent for dehydration
At last, with the weight ratio of the poly-repelling crude oil demulsifying agent for dehydration of preparation is that 10～45% A tensio-active agent, weight ratio are that 5～50% B tensio-active agent and weight ratio are that 10～45% C tensio-active agent places the enamel still that is mixed successively, start stirring, be warming up to 50 ± 5 ℃, slowly drip weight ratio and be after 20～45% methyl alcohol and weight ratio be 10～25% water, stir 30～60min, cooling discharge obtains poly-repelling crude oil demulsifying agent for dehydration.
Beneficial effect of the present invention: raw material and preparation technology that the poly-repelling crude oil demulsifying agent for dehydration of the present invention adopts, different with existing emulsion splitter, its breaking emulsion and dewatering effect obviously is better than existing emulsion splitter.In the dehydrating of crude oil rules, the produced fluid dewatering demulsifier for accumulating and repelling crude oil dosage is few, and it is moisture less than 0.2% that crude oil takes off the back, and sewage with oil is less than 50mg/l.Make crude oil take off moisture the meeting the requirements in back, and oleaginousness is reduced to below the 50mg/l in the sewage from more than the 5500mg/l.
Embodiment
In the present embodiment, the raw material that is adopted is technical grade, adds than all being weight percentage.
One, the preparation of A tensio-active agent
13.2% the full-fluorine octyl sulfuryl fluoride initiator of preparation intermediate PEA is placed the 1500L stainless steel cauldron, start stirring, be warming up to 120 ± 5 ℃, find time, fill nitrogen, the oxyethane of slow dropping 86.8%, reaction pressure is controlled at 0.2～0.4MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained intermediate PEA.
52.3% intermediate PEA and 0.13% potassium hydroxide of preparation A tensio-active agent are placed the 1500L stainless steel cauldron, start stirring, be warming up to 130 ± 5 ℃, find time, fill nitrogen, the propylene oxide of slow dropping 47.57%, reaction pressure is controlled at 0.2～0.4MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained the A tensio-active agent.
Two, the preparation of B tensio-active agent
47.8% the phenolic resin initiator of preparation intermediate PEB is placed the 1500L stainless steel cauldron, start stirring, be warming up to 125 ± 5 ℃, find time, fill nitrogen, the oxyethane of slow Dropwise 5 2.2%, reaction pressure is controlled at 0.2～0.4MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained intermediate PEB.
45.6% intermediate PEB and 0.15% potassium hydroxide of preparation B tensio-active agent are placed the 1500L stainless steel cauldron, start stirring, be warming up to 135 ± 5 ℃, find time, fill nitrogen, the propylene oxide of slow Dropwise 5 4.25%, reaction pressure is controlled at 0.2～0.5MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained the B tensio-active agent.
Three, the preparation of C tensio-active agent
43.5% the phenol amine resin initiator of preparation intermediate PEC is placed the 1500L stainless steel cauldron, start stirring, be warming up to 125 ± 5 ℃, find time, fill nitrogen, the oxyethane of slow Dropwise 5 6.5%, reaction pressure is controlled at 0.2～0.4MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained intermediate PEC.
50% intermediate PEC and 0.11% potassium hydroxide of preparation C tensio-active agent are placed the 1500L stainless steel cauldron, start stirring, be warming up to 135 ± 5 ℃, find time, fill nitrogen, the propylene oxide of slow dropping 49.89%, reaction pressure is controlled at 0.2～0.4MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained the C tensio-active agent.
Four, the preparation of poly-repelling crude oil demulsifying agent for dehydration
The C tensio-active agent of the B tensio-active agent of the A tensio-active agent of 405kg, 360kg and 225kg is placed the 2000L enamel still that is mixed successively, start stirring, be warming up to 50 ± 5 ℃, after slowly dripping the methyl alcohol and 180kg softening water of 630kg, stir 30～60min, cooling discharge obtains poly-repelling crude oil demulsifying agent for dehydration 1800kg.
Rig-site utilization experiment in 2005 contains polyacrylamide 312.5mg/l in extraction liquid, the produced fluid dewatering demulsifier for accumulating and repelling crude oil that the The Zhaozhou Bridge field use present embodiment of water apparent viscosity 7.43S-1 (40 ℃) is produced carries out breaking emulsion and dewatering and handles.The produced fluid dewatering demulsifier for accumulating and repelling crude oil dosage is when 80-150mg/l, and is moisture less than 0.2% after the dehydrating of crude oil, and sewage separates the back oil-containing less than 50mg/l.The dehydrating of crude oil effect obviously is better than common emulsion splitter, make crude oil take off the moisture conformance with standard requirement in back, and oleaginousness is reduced to below the 50mg/l in the sewage from more than the 5500mg/l.
Claims (2)
1, a kind of produced fluid dewatering demulsifier for accumulating and repelling crude oil is characterized in that: formulation weight per-cent is: A tensio-active agent, 10～45%; The B tensio-active agent, 5～50%; The C tensio-active agent, 10～45%; Methyl alcohol, 20～45%; Water, 10～25%, wherein:
The raw material weight per-cent of A tensio-active agent is: intermediate PEA, 15～59%; Potassium hydroxide, 0.1～0.25%; Propylene oxide, 40～84%, A tensio-active agent raw material all components and be 100%, wherein: the raw material weight per-cent of preparation intermediate PEA is: full-fluorine octyl sulfuryl fluoride, 10-65%; Oxyethane, 35-90%,
The raw material weight per-cent of B tensio-active agent is: intermediate PEB, 20～59%; Potassium hydroxide, 0.1～0.25%; Propylene oxide, 40～79%, B tensio-active agent raw material all components and be 100%, wherein: the raw material weight per-cent of preparation intermediate PEB is: phenolic resin, 10-70%; Oxyethane, 30-90%,
The raw material weight per-cent of C tensio-active agent is: intermediate PEC, 15～64%; Potassium hydroxide, 0.1～0.25%; Propylene oxide, 35～84%, C tensio-active agent raw material all components and be 100%, wherein: the raw material weight per-cent of preparation intermediate PEC is: phenol amine resin, 14-68%; Oxyethane, 32-86%.
2, a kind of preparation method of produced fluid dewatering demulsifier for accumulating and repelling crude oil is characterized in that: by the raw material weight per-cent batching of prescription, being divided into following four steps carries out:
One, the preparation of A tensio-active agent
At first, with the weight percent of preparation intermediate PEA is that 10%-65% full-fluorine octyl sulfuryl fluoride is that initiator places stainless steel cauldron, start stirring, be warming up to 120 ± 5 ℃, find time, fill nitrogen, slowly drip weight ratio and be 35%-90% oxyethane, reaction pressure is controlled at 0.2～0.5MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained intermediate PEA
With the weight ratio of preparation A tensio-active agent is that 15%～59% intermediate PEA and weight ratio are that 0.1%～0.25% potassium hydroxide places stainless steel cauldron, start stirring, be warming up to 130 ± 5 ℃, find time, fill nitrogen, slowly the dropping weight ratio is 40%～84% propylene oxide, reaction pressure is controlled at 0.2～0.5MPa, dropwises, after question response still internal pressure returns zero, cooling discharge obtains the A tensio-active agent, A tensio-active agent raw material all components and be 100%;
Two, the preparation of B tensio-active agent
At first, with the weight ratio of preparation intermediate PEB is that 10-70% phenolic resin initiator places stainless steel cauldron, start stirring, be warming up to 125 ± 5 ℃, find time, fill nitrogen, slowly drip weight ratio and be 30%～90% oxyethane, reaction pressure is controlled at 0.2～0.5MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained intermediate PEB
With the weight ratio of preparation B tensio-active agent is that 20%～59% intermediate PEB and weight ratio are that 0.1～0.25% potassium hydroxide places stainless steel cauldron, start stirring, be warming up to 135 ± 5 ℃, find time, fill nitrogen, slowly the dropping weight ratio is 40%～79% propylene oxide, reaction pressure is controlled at 0.2～0.5MPa, dropwises, after question response still internal pressure returns zero, cooling discharge obtains the B tensio-active agent, B tensio-active agent raw material all components and be 100%;
Three, the preparation of C tensio-active agent
At first, with the weight ratio of preparation intermediate PEC is that 14-68% phenol amine resin initiator places stainless steel cauldron, start stirring, be warming up to 120 ± 5 ℃, find time, fill nitrogen, slowly drip weight ratio and be 32%～86% oxyethane, reaction pressure is controlled at 0.2～0.5MPa, dropwise, after question response still internal pressure returned zero, cooling discharge obtained intermediate PEC
With the weight ratio of preparation C tensio-active agent is that 15%～64% intermediate PEC and weight ratio are that 0.1～0.25% potassium hydroxide places stainless steel cauldron, start stirring, be warming up to 135 ± 5 ℃, find time, fill nitrogen, slowly the dropping weight ratio is 35%～84% propylene oxide, reaction pressure is controlled at 0.2～0.5MPa, dropwises, after question response still internal pressure returns zero, cooling discharge obtains the C tensio-active agent, C tensio-active agent raw material all components and be 100%;
Four, the preparation of poly-repelling crude oil demulsifying agent for dehydration
At last, with the weight ratio of the poly-repelling crude oil demulsifying agent for dehydration of preparation is that the C tensio-active agent of 10～45% A tensio-active agent, 5～50% B tensio-active agent and 10～45% places the enamel still that is mixed successively, start stirring, be warming up to 50 ± 5 ℃, slowly drip weight ratio and be after 20～45% methyl alcohol and weight ratio be 10～25% water, stir 30～60min, cooling discharge obtains poly-repelling crude oil demulsifying agent for dehydration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB200610064907XA CN100513526C (en) | 2006-03-17 | 2006-03-17 | Dehydration demulsifier for produced liquid of polymer flooding crude oil |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200610064907XA CN100513526C (en) | 2006-03-17 | 2006-03-17 | Dehydration demulsifier for produced liquid of polymer flooding crude oil |
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| CN1834208A CN1834208A (en) | 2006-09-20 |
| CN100513526C true CN100513526C (en) | 2009-07-15 |
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| CN101671573B (en) * | 2009-10-10 | 2013-06-19 | 山东德仕化工集团有限公司 | Production formula of DSP-1 crude oil demulsifier |
| CN105505447A (en) * | 2015-12-07 | 2016-04-20 | 山西潞安煤基合成油有限公司 | Method for rapidly separating oil and water produced through Fischer-Tropsch synthesis |
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