CN1177768C - Flocculant for oil-containing sewage low-temp. treatment in oil field - Google Patents
Flocculant for oil-containing sewage low-temp. treatment in oil field Download PDFInfo
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- CN1177768C CN1177768C CNB021324263A CN02132426A CN1177768C CN 1177768 C CN1177768 C CN 1177768C CN B021324263 A CNB021324263 A CN B021324263A CN 02132426 A CN02132426 A CN 02132426A CN 1177768 C CN1177768 C CN 1177768C
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- titanium tetrachloride
- flocculant
- oil
- flocculation agent
- water
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Abstract
The present invention relates to a flocculant for oily sewage low-temperature treatment in an oil field, particularly to a flocculant prepared by taking titanium tetrachloride as a main ingredient. The concentration of the titanium tetrachloride in the flocculant is from 1% to 50%, the flocculant can be a water solution of the titanium tetrachloride or an alcoholic solution of the titanium tetrachloride, and the concentration of the titanium tetrachloride in the solution is from 20% to 50%. The flocculant can also be a novel flocculant prepared from the ingredients of the following weight percentages: 1% to 15% of titanium tetrachloride, 0.05% to 1% of cationic quaternary ammonium salt type polyacrylamide flocculant, 1% to 20% of polyoxyethylene trimethyl ammonium chloride, 0.05% to 1% of polydimethyl diallyl ammonium chloride, 5% to 30% of aluminium polychloride and 50% to 92% of water. The flocculant is not sensitive to the temperature, the pH value and the mineralizing degree of sewage with good flocculating effect.
Description
Technical field: the present invention relates to a kind of flocculation agent, the flocculation agent that particularly a kind of oil-contaminated water of oil field is handled.
Background technology: flocculation agent is to make suspended solid gathering in the water and the chemical agent that floats or sink by action of gravity.The existence of crude oil flowability improver in the reduction of oil-contaminated water of oil field treatment temp and the sewage at present increases the sewage disposal difficulty greatly, only depends on oil field sedimentation commonly used, the needs that filtration treatment technology can not satisfy the processing of low temperature oil-contaminated water.Therefore need add targetedly flocculation agent handles oily(waste)water.The flocculation agent that is used for the oil-contaminated water of oil field processing at present comprises: aluminium salt, molysite and natural macromolecule flocculating agent, treated starch synthetic polymeric flocculant, linear macromolecules such as polyacrylamide and homologue, derivative.According to the action principle of inorganic flocculating agent, flocculation agent dissociates in the aqueous solution and the ion that forms, and its electric density is big more, and ion volume is more little, and flocculating effect is good more, and its ratio increases progressively with geometricprogression.Therefore, in inorganic flocculating agent, have only just tervalent aluminium, iron plasma to have throwing out, the sodium of monovalence or divalence, magnesium, calcium plasma then do not have throwing out basically.In industrial application, again with polymerizations such as aluminium, iron, to obtain higher electric density.But volume increases after the polymerization, its sterically hindered also increase, so its flocculating effect is compared the increase that does not obtain geometricprogression with monomer.And existing flocculation agent is very sensitive to temperature, pH value and the salinity of oily(waste)water, and flocculating effect is bad.
Summary of the invention: the invention provides a kind of flocculation agent that is used for the oil-contaminated water of oil field subzero treatment.This flocculation agent has solved existing flocculation agent to temperature, pH value and the salinity of oily(waste)water sensitive issue too.The present invention is to be the flocculation agent that main composition is made with titanium tetrachloride, and the concentration of titanium tetrachloride is 1～50% in the flocculation agent.This flocculation agent can be the aqueous solution or the alcoholic solution of titanium tetrachloride, and the concentration of titanium tetrachloride is 20～50% in the solution, and used alcohol can be methyl alcohol or ethanol; Or the flocculation agent of making by titanium tetrachloride, cation quaternary ammonium salt type polyacrylamide flocculant, polyoxyethylene trimethyl ammonium chloride, Poly Dimethyl Diallyl Ammonium Chloride, polymerize aluminum chloride and water, flocculation agent is made up of following raw materials by weight percent: water 50～92, titanium tetrachloride 1～15, cation quaternary ammonium salt type polyacrylamide flocculant 0.05～1, polyoxyethylene trimethyl ammonium chloride 1～20, Poly Dimethyl Diallyl Ammonium Chloride 0.05～1, polymerize aluminum chloride 5～30.Titanium tetrachloride is inorganic strong cation flocculation agent, and it is the higher ion of valence state, and its ionic radius is also much smaller than just tervalent iron ion, and is approaching with aluminum ion, thereby its flocculating effect is more much better than poly-aluminium, poly-iron.This flocculation agent is good to cryogenic adaptability, and the effect that can also play flocculation nuclear and transfer pH value in water.Flocculation agent system of the present invention all has good throwing out to the oil in water emulsion and the mechanical impurity of the various size in the oily(waste)water, and is insensitive to temperature, pH value and the salinity of oily(waste)water, and the bacterium in the oily(waste)water is also had germicidal action.During novel flocculant industrial application of the present invention, its dosage is generally 10～200mg/L, and the result of use when wherein dosage is 10～30mg/L is better.The using method of flocculation agent of the present invention is: flocculation agent directly can be added in the oily(waste)water, also add behind the dilutable water again, Dilution ratio is determined according to the industry spot practical situation.Carry out the on-the-spot simultaneous test of industrialness with novel flocculant of the present invention at the Daqing oil field five factory's apricot 15-I joint stations that recover the oil, experimental session water quality situation is as follows: pH value is 8.4, total mineralization is 5138mg/L, treatment temp is 31～32 ℃, particle diameter is less than 50 μ m, the oil droplet volume accounts for 82.4% of cumulative volume, belongs to high emulsification oily(waste)water, and contrast agents is a polymerize aluminum chloride.Its test-results sees Table one, as can be seen from the test results, adopts flocculation agent of the present invention, and its wastewater treatment efficiency will be far superior to polymerize aluminum chloride, adds the needs that 18mg/L can satisfy field produces.
Table one:
| Medicament title and dosage | Oil content of wastewater mg/L | Suspended solids content mg/L | Median particle size μ m | ||||||||||
| Come water | Sedimentation | Filter tank | One filter | Two filters | Come water | Sedimentation | Filter tank | One filter | Two filters | Filter tank | One filter | Two filters | |
| 41 ℃ of blank tests | 114 | 50.2 | 17.2 | 17.0 | 7.27 | 125 | 73.8 | 28.0 | 20.6 | 17.9 | 3.9 | 3.7 | 2.5 |
| 31 ℃ of blank tests | 119 | 104 | 31.3 | 24.1 | 15.4 | 105 | 92.5 | 35.0 | 27.2 | 22.3 | 4.1 | 4.0 | 3.2 |
| Polymerize aluminum chloride 30mg/L | 109 | 45.0 | 15.3 | 8.52 | 4.31 | 126 | 56.0 | 20.3 | 16.5 | 13.7 | 3.5 | 3.1 | 2.4 |
| Efficient flocculant 18mg/L | 139 | 21.9 | 5.11 | 0.21 | Vestige | 141 | 34.0 | 7.46 | 4.06 | 2.89 | 2.8 | 1.5 | 1.4 |
Embodiment one: the flocculation agent of present embodiment is the aqueous solution of titanium tetrachloride, and the concentration of titanium tetrachloride is 20～35%.
Embodiment two: the flocculation agent of present embodiment is the aqueous solution of titanium tetrachloride, and the concentration of titanium tetrachloride is 35～50%.
Embodiment three: the flocculation agent of present embodiment is the solution that titanium tetrachloride and methyl alcohol are made into, and the concentration of titanium tetrachloride is 20～35%.
Embodiment four: the flocculation agent of present embodiment is the solution that titanium tetrachloride and ethanol are made into, and the concentration of titanium tetrachloride is 35～50%.
Embodiment five: the flocculation agent of present embodiment is made up of following raw materials by weight percent: water 75～79, titanium tetrachloride 5～10, cation quaternary ammonium salt type polyacrylamide flocculant 0.1～0.5, polyoxyethylene trimethyl ammonium chloride 5～15, Poly Dimethyl Diallyl Ammonium Chloride 0.1～0.5, polymerize aluminum chloride 10～20.The compound method of above-mentioned flocculation agent is: heat water to 50～70 ℃, the best is 60 ℃, adds cation quaternary ammonium salt type polyacrylamide flocculant and Poly Dimethyl Diallyl Ammonium Chloride then, stirs 2～4h; Add polyoxyethylene trimethyl ammonium chloride and titanium tetrachloride again, stir 15～30min, stop heating, add polymerize aluminum chloride at last, stir 0.5～2h, promptly get the finished product.The general formula of above-mentioned cation quaternary ammonium salt type polyacrylamide flocculant is (C
3H
5NO) m (C
6H
12NOCl) n, its relative molecular weight are 4 * 10
6～6 * 10
6The general formula of polyoxyethylene trimethyl ammonium chloride is (C
3H
5OCl) x (C
6H
14NOCl) y, x+y=400 in the formula～500, y: x=1: 2, its relative molecular weight is 6 * 10
4～1 * 10
6The general formula of Poly Dimethyl Diallyl Ammonium Chloride is (C
8H
16NCl) x, its relative molecular weight are 1 * 10
6～3 * 10
6The general formula of polymerize aluminum chloride is [Al
2(OH)
nCl
6-nXH
2O] m, m in the formula≤10, n=1～5.
Embodiment six: the flocculation agent of present embodiment is made up of following raw materials by weight percent: water 80～92, titanium tetrachloride 1～5, cation quaternary ammonium salt type polyacrylamide flocculant 0.05～0.1, polyoxyethylene trimethyl ammonium chloride 1～5, Poly Dimethyl Diallyl Ammonium Chloride 0.05～0.1, polymerize aluminum chloride 5～10.Its manufacture method is identical with embodiment five.
Embodiment seven: the flocculation agent of present embodiment is made up of following raw materials by weight percent: water 50～54, titanium tetrachloride 10～15, cation quaternary ammonium salt type polyacrylamide flocculant 0.5～1, polyoxyethylene trimethyl ammonium chloride 15～20, Poly Dimethyl Diallyl Ammonium Chloride 0.5～1, polymerize aluminum chloride 20～30.Its manufacture method is identical with embodiment five.
Claims (6)
1, the flocculation agent that is used for the oil-contaminated water of oil field subzero treatment, it is characterized in that it is is main composition and by titanium tetrachloride with titanium tetrachloride, cation quaternary ammonium salt type polyacrylamide flocculant, the polyoxyethylene trimethyl ammonium chloride, Poly Dimethyl Diallyl Ammonium Chloride, the flocculation agent that polymerize aluminum chloride and water are made, flocculation agent is made up of following raw materials by weight percent: water 50～92, titanium tetrachloride 1～15, cation quaternary ammonium salt type polyacrylamide flocculant 0.05～1, polyoxyethylene trimethyl ammonium chloride 1～20, Poly Dimethyl Diallyl Ammonium Chloride 0.05～1, polymerize aluminum chloride 5～30.
2, the flocculation agent that is used for the oil-contaminated water of oil field subzero treatment according to claim 1 is characterized in that it is made up of following raw materials by weight percent: water 75～79, titanium tetrachloride 5～10, cation quaternary ammonium salt type polyacrylamide flocculant 0.1～0.5, polyoxyethylene trimethyl ammonium chloride 5～15, Poly Dimethyl Diallyl Ammonium Chloride 0.1～0.5, polymerize aluminum chloride 10～20.
3, the flocculation agent that is used for the oil-contaminated water of oil field subzero treatment according to claim 1 is characterized in that it is made up of following raw materials by weight percent: water 80～92, titanium tetrachloride 1～5, cation quaternary ammonium salt type polyacrylamide flocculant 0.05～0.1, polyoxyethylene trimethyl ammonium chloride 1～5, Poly Dimethyl Diallyl Ammonium Chloride 0.05～0.1, polymerize aluminum chloride 5～10.
4, the flocculation agent that is used for the oil-contaminated water of oil field subzero treatment according to claim 1 is characterized in that it is made up of following raw materials by weight percent: water 50～54, titanium tetrachloride 10～15, cation quaternary ammonium salt type polyacrylamide flocculant 0.5～1, polyoxyethylene trimethyl ammonium chloride 15～20, Poly Dimethyl Diallyl Ammonium Chloride 0.5～1, polymerize aluminum chloride 20～30.
5, the flocculation agent that is used for the oil-contaminated water of oil field subzero treatment is characterized in that this flocculation agent is the aqueous solution or the alcoholic solution of titanium tetrachloride, and the concentration of titanium tetrachloride is 20～50% in the solution.
6, the flocculation agent that is used for the oil-contaminated water of oil field subzero treatment according to claim 5 is characterized in that used alcohol can be methyl alcohol or ethanol.
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| CNB021324263A CN1177768C (en) | 2002-06-06 | 2002-06-06 | Flocculant for oil-containing sewage low-temp. treatment in oil field |
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|---|---|---|---|
| CNB021324263A CN1177768C (en) | 2002-06-06 | 2002-06-06 | Flocculant for oil-containing sewage low-temp. treatment in oil field |
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| CN1177768C true CN1177768C (en) | 2004-12-01 |
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Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701387A (en) * | 2012-06-27 | 2012-10-03 | 山东大学 | Titanium tetrachloride-poly dimethyl diallyl ammonium chloride inorganic-organic compound flocculant and preparation method thereof |
| CN102976462B (en) * | 2012-12-20 | 2013-09-25 | 山东大学 | Preparation method of inorganic polymeric flocculant titanium tetrachloride |
| CN103351065B (en) * | 2013-07-05 | 2016-01-20 | 玉林市兰科铸造环保设备有限公司 | The method of wastewater treatment of mixed type cast waste sand wet reclamation |
| CA2942910A1 (en) * | 2014-03-20 | 2015-09-24 | Alberta Innovates - Technology Futures | Inorganic particle polymer hybrids and uses thereof |
| CN103964554B (en) * | 2014-04-18 | 2015-10-21 | 同济大学 | Polyaluminum sulfate titanium-polydimethyldiallylachloride chloride composite coagulant and preparation and application method thereof |
| CN104071857B (en) * | 2014-07-17 | 2015-09-02 | 天津亿利科能源科技发展股份有限公司 | A kind of preparation method of oil field low temperature viscous crude oily water treatment water cleaning agent |
| CN104261529B (en) * | 2014-09-19 | 2015-12-02 | 句容亿格纳米材料厂 | A kind of Nanometer Titanium Dioxide powder coating flocculation agent and preparation method thereof |
| CN105883997A (en) * | 2016-06-22 | 2016-08-24 | 陈朝民 | Flocculating agent for sewage and method for preparing flocculating agent |
| CN105858979A (en) * | 2016-06-24 | 2016-08-17 | 李嘉 | Beneficiation wastewater treatment method |
| CN107176661B (en) * | 2017-07-17 | 2020-12-22 | 湖南科技大学 | Preparation method and application of poly-titanium aluminum chloride-cationic polyacrylamide composite flocculant |
| CN107840428A (en) * | 2017-11-17 | 2018-03-27 | 侯英 | High-efficiency sewage flocculant and preparation method thereof |
| CN110015774A (en) * | 2018-01-09 | 2019-07-16 | 中国石油天然气股份有限公司 | Rapid petrochemical wastewater treatment method |
| CN108483606B (en) * | 2018-04-12 | 2020-10-16 | 浙江恒祥棉纺织造有限公司 | Textile sewage impurity coagulant and preparation method thereof |
| CN109111944A (en) * | 2018-08-15 | 2019-01-01 | 黑龙江莱睿普思环境科技发展有限公司 | The efficient flocculant and preparation method thereof of waste mineral oil purification |
| CN109530097B (en) * | 2018-11-14 | 2021-02-02 | 安徽工业大学 | Selective flocculation flotation method for micro-fine particle hematite |
| CN110420482B (en) * | 2019-08-14 | 2022-04-05 | 中国特种设备检测研究院 | Composite flocculant for treating oil sand mine tailings and method for treating mature fine tailings |
| CN113979601B (en) * | 2021-11-24 | 2023-09-19 | 杭州大地海洋环保股份有限公司 | Greasy dirt waste water treatment method |
| CN115403610A (en) * | 2022-08-31 | 2022-11-29 | 宁夏长城水务有限责任公司 | Organic titanium salt flocculating agent and preparation method thereof |
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