CN108128877B - Synthetic method of demulsification and water purification integrated agent - Google Patents
Synthetic method of demulsification and water purification integrated agent Download PDFInfo
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- CN108128877B CN108128877B CN201711394387.3A CN201711394387A CN108128877B CN 108128877 B CN108128877 B CN 108128877B CN 201711394387 A CN201711394387 A CN 201711394387A CN 108128877 B CN108128877 B CN 108128877B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 238000000746 purification Methods 0.000 title claims abstract description 21
- 238000010189 synthetic method Methods 0.000 title claims abstract description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000002091 cationic group Chemical group 0.000 claims abstract description 21
- 229920002755 poly(epichlorohydrin) Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 9
- 229920000570 polyether Polymers 0.000 claims abstract description 9
- 150000003141 primary amines Chemical class 0.000 claims abstract description 9
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims 1
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims 1
- IMENJLNZKOMSMC-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCN IMENJLNZKOMSMC-UHFFFAOYSA-N 0.000 claims 1
- RUSNFULRUJHOPI-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCNCCN RUSNFULRUJHOPI-UHFFFAOYSA-N 0.000 claims 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 13
- 239000010865 sewage Substances 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000003921 oil Substances 0.000 description 15
- 238000010992 reflux Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- -1 quaternary ammonium salt cation Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/682—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of chemical compounds for dispersing an oily layer on water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Landscapes
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a method for synthesizing a demulsification and water purification integrated agent. The synthesis method comprises the following steps: firstly, polyepichlorohydrin is respectively reacted with primary amine and tertiary amine in sequence to obtain a polyether cationic intermediate, and then the intermediate is reacted with carbon disulfide to obtain the amphoteric demulsifying and water purifying integrated agent. The demulsification and water purification integrated agent product obtained by the synthetic method has good water purification effect, compact floc, no conglutination and clear water quality, and is particularly suitable for polymer-containing sewage treatment.
Description
Technical Field
The invention relates to the technical field of sump oil water treatment, in particular to a synthesis method of a demulsification and water purification integrated agent.
Background
With the continuous deep development of oil fields and the application of tertiary oil recovery technology, the water content of crude oil gradually rises, the comprehensive water content of part of crude oil in the oil fields is higher than 90 percent, but the treatment of polymer-containing oil recovery sewage generated in the oil recovery process is always a difficult problem. The polymer monomer has the characteristics of good dispersion, emulsification, adsorption and the like, so that oil-water emulsification is aggravated, the amount of suspended matters such as carried mud and the like is increased, an emulsion becomes complex and stable, and crude oil demulsification and dehydration are difficult. At each stage of equipment containing polymer sewage treatment process, polymer precipitation and cementation influence is generated, so that pollution and blockage are serious, the equipment is frequently cleaned, and the treatment effect of the equipment is influenced. The existing water purifying agent can not completely meet the treatment requirement of polymer-containing effluent, the agent dehydration time still needs more than 30min, and meanwhile, the compatibility of chemical agents and polymers is not ideal, intermolecular interaction occurs, so that the polymers are separated out, and viscoelastic jelly is gradually formed after the polymer is combined with oil sludge. The viscoelastic jelly circulates in the system, so that the treatment process is seriously polluted and blocked, the cleaning difficulty is high, and the treatment effect of the whole process is influenced. Therefore, the development of novel agents for treating polymer flooding oil extraction wastewater is an urgent problem to be solved for stable development of oil fields.
Chinese patent application CN201510902507.0 discloses a chemical treatment method for polymer-containing sewage. 1) Adding a cationic water clarifier into the polymer-containing sewage, and uniformly mixing; 2) adding a non-ionic water clarifier into the sewage treated in the step 1), and uniformly mixing; 3) and (3) adding a weak cationic water clarifier to the sewage treated in the step 2) in a gathering manner, and uniformly mixing to realize the purification of the polymer-containing sewage. The method of 'graded addition and combined treatment' provided by the invention realizes the optimized matching of the functional characteristics of the water clarifier and the sewage property, but the labor cost is increased by adding the agent for many times, and an integrated agent with good effect needs to be developed.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a synthesis method of the demulsification and water purification integrated agent, which has the advantages of good chemical and thermal stability, wide application range, small dosage of the agent, high demulsification speed, compact floc, easy sump oil recovery and no secondary pollution.
The invention realizes the technical problems through the following technical scheme.
The invention relates to a synthesis method of a demulsification and water purification integrated agent, which comprises the following process steps:
1) synthesis of polyether cationic intermediate
Adding primary amine and an alcohol-water solvent into a four-neck flask with a thermometer, a reflux condenser and a speed-regulating stirrer in a metered manner, wherein the mass ratio of the alcohol to the water is 1: 1-1: 1.5, and the primary amine and the alcohol-water solvent account for 25-45% of the mass of the total reaction system; stirring, dropwise adding polyepichlorohydrin, controlling the temperature to be 30-45 ℃, and controlling the reaction molar ratio of the primary amine to the polyepichlorohydrin to be 1: 0.5-1: 0.7. After the polyepichlorohydrin is dripped, heating to 45-50 ℃, preserving the heat for 1-2h, and measuring the Grignard viscosity to 0.8-1.2 seconds;
adding tertiary amine to continue reacting, wherein the reaction molar ratio of the tertiary amine to the primary amine is 0.4: 1-0.65: 1, the reaction temperature is 100-105 ℃, and the reaction time is 2-4h, so as to obtain a reddish brown transparent water-soluble product;
2) synthesis of demulsification and water purification integrated agent
Adding a cationic intermediate and deionized water into a reaction device according to the mass ratio of 3.5:1-6.5: 1; slowly dropwise adding carbon disulfide and alkali liquor, and controlling the reaction temperature to be 0-25 ℃; controlling the dropping speed of the alkali liquor to be higher than that of the carbon disulfide, and controlling the pH value of the reaction liquid to be 8.5-12; after the dropwise addition, the temperature is raised to 35-45 ℃, the reaction is continued for 3-5h, the temperature is reduced, and the material is discharged, so that an orange red transparent liquid is obtained, wherein the reaction molar ratio of the cationic intermediate to the carbon disulfide is 1: 2.0-1: 3.5.
The invention relates to a synthesis method of a demulsification and water purification integrated agent, which has the following characteristics: (1) the water-soluble quaternary ammonium salt cation and dithiocarbamate anion special structure has good chemical and thermal stability, and wide applicable pH range and temperature range; (2) the structure contains hydrophilic lipophilic group, and the surfactant which can replace an oil-water interface is added into the oil-containing polluted oil water to destabilize the emulsion and realize demulsification; (3) the special net structure has the bridging sweeping function to form compact and non-viscoelastic flocs, so that the water quality is clear; (4) the polymer can be used with anionic polymers and cationic polymers, and has wide application range; (5) the anion and cation groups have obvious synergistic effect in the water treatment process. Compared with the prior art, the beneficial effects are that: the demulsifier integrated agent synthesized by the synthesis method has the advantages of small dosage of agent, high demulsification speed and compact floc, not only improves the oil removal efficiency, but also is beneficial to the recovery of dirty oil, and avoids the problem of secondary pollution caused by a large amount of sludge generated by the traditional flocculant.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The method comprises the following steps: synthesis of polyether cationic intermediate
Adding diethylenetriamine (41.27g, 0.4mol) and a methanol-water solvent (72g, the content of methanol is 30 percent) into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; starting stirring, dropwise adding polyepichlorohydrin (18.5g, 0.2mol), and controlling the reaction temperature to be 30-45 ℃; after the polyepichlorohydrin is dripped, the temperature is raised to 50 ℃, the temperature is kept for 1.5h, and the Grignard viscosity is measured and reaches 0.9 second. Then adding 33% trimethylamine (28.66g, 0.16mol), controlling the reaction temperature at 100-105 ℃, and continuing the reaction for 2h to obtain the reddish brown transparent water-soluble product.
Step two: synthesis of demulsification and water purification integrated agent
160g of cationic intermediate and 36g of deionized water are metered into a four-neck flask with a thermometer, a reflux condenser and a speed-regulating stirrer; slowly dropwise adding carbon disulfide (60.8g, 0.8mol) and 40% sodium hydroxide aqueous solution, and controlling the reaction temperature to be 0-25 ℃; controlling the dropping speed of the sodium hydroxide aqueous solution to be higher than that of the carbon disulfide, and controlling the pH value of the reaction solution to be 9-11; after the dropwise addition, the temperature is raised to 30 ℃, the reaction is continued for 4 hours, and the temperature is lowered for discharging to obtain 261g of orange-red transparent liquid.
Example 2
The method comprises the following steps: synthesis of polyether cationic intermediate
Adding diethylenetriamine (41.27g, 0.4mol) and a methanol-water solvent (72g, the content of methanol is 30 percent) into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; starting stirring, dropwise adding polyepichlorohydrin (18.5g, 0.2mol), and controlling the reaction temperature to be 30-45 ℃; after the dripping of the polyepichlorohydrin is finished, heating to 50 ℃, preserving the heat for 1.5h, and measuring the Grignard viscosity until the viscosity reaches 00.9 seconds. Then adding 33 percent trimethylamine (39g, 0.22mol), controlling the reaction temperature to be 100-105 ℃, and continuing the reaction for 3 hours to obtain the reddish brown transparent water-soluble product.
Step two: synthesis of demulsification and water purification integrated agent
170g of cationic intermediate and 36g of deionized water are metered into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; slowly dropwise adding carbon disulfide (85g, 1.12mol) and 40% sodium hydroxide aqueous solution, and controlling the reaction temperature to be 0-25 ℃; controlling the dropping speed of the sodium hydroxide aqueous solution to be higher than that of the carbon disulfide, and controlling the pH value of the reaction solution to be 9-11; after the dropwise addition, the temperature is raised to 30 ℃, the reaction is continued for 4.5 hours, and the temperature is reduced and the material is discharged, so that 331g of orange-red transparent liquid is obtained.
Example 3
The method comprises the following steps: synthesis of polyether cationic intermediate
Triethylene tetramine (50.49g, 0.4mol) and a methanol-water solvent (103.6g, the methanol content is 35%) are added into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; starting stirring, dropwise adding polyepichlorohydrin (22.2g, 0.24mol), and controlling the reaction temperature to be 30-45 ℃; after the polyepichlorohydrin is dripped, the temperature is raised to 50 ℃, the temperature is kept for 2 hours, the Grignard viscosity is measured, and the viscosity reaches 1.0 second. Then adding 33% trimethylamine (35.8g, 0.2mol), controlling the reaction temperature at 100-105 ℃, and continuing the reaction for 2.5h to obtain the reddish brown transparent water-soluble product.
Step two: synthesis of demulsification and water purification integrated agent
212g of cationic intermediate and 34.5g of deionized water are metered into a four-neck flask with a thermometer, a reflux condenser and a speed-regulating stirrer; slowly dropwise adding carbon disulfide (60.8g, 0.8mol) and 40% sodium hydroxide aqueous solution, and controlling the reaction temperature to be 0-25 ℃; controlling the dropping speed of the sodium hydroxide aqueous solution to be higher than that of the carbon disulfide, and controlling the pH value of the reaction solution to be 8-12; after the dropwise addition, the temperature is raised to 35 ℃, the reaction is continued for 4 hours, and the temperature is lowered for discharging to obtain 345g of orange-red transparent liquid.
Example 4
The method comprises the following steps: synthesis of polyether cationic intermediate
Adding diethylenetriamine (41.27g, 0.4mol) and a methanol-water solvent (110g, the content of methanol is 35 percent) into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; starting stirring, dropwise adding polyepichlorohydrin (32g, 0.35mol), and controlling the reaction temperature to be 30-45 ℃; after the polyepichlorohydrin is dripped, the temperature is raised to 50 ℃, the temperature is kept for 1.5h, and the Grignard viscosity is measured and reaches 0.9 second. Then adding 33 percent trimethylamine (39.41g, 0.2mol), controlling the reaction temperature to be 100-105 ℃, and continuing the reaction for 2.5h to obtain the reddish brown transparent water-soluble product.
Step two: synthesis of demulsification and water purification integrated agent
222g of cationic intermediate and 55g of deionized water are metered into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; slowly dropwise adding carbon disulfide (85.12g, 1.12mol) and 40% potassium hydroxide aqueous solution, and controlling the reaction temperature to be 0-25 ℃; controlling the dropping speed of the potassium hydroxide aqueous solution to be higher than that of the carbon disulfide, and controlling the pH value of the reaction solution to be 9-11; after the dropwise addition, the temperature is raised to 40 ℃, the reaction is continued for 4 hours, and the temperature is lowered for discharging to obtain 402g of orange-red transparent liquid.
Example 5
The method comprises the following steps: synthesis of polyether cationic intermediate
Adding triethylene tetramine (50.49g, 0.4mol) and an ethanol-water solvent (95.37g, ethanol content is 30%) into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; starting stirring, dropwise adding polyepichlorohydrin (22.2g, 0.24mol), and controlling the reaction temperature to be 30-45 ℃; after the polyepichlorohydrin is dripped, the temperature is raised to 50 ℃, the temperature is kept for 2 hours, the Grignard viscosity is measured, and the viscosity reaches 1.0 second. And triethylamine (20.24g, 0.2mol) is added, the reaction temperature is controlled to be 100-105 ℃, and the reaction is continued for 3.5h, so that a reddish brown transparent water-soluble product is obtained.
Step two: synthesis of demulsification and water purification integrated agent
188g of cationic intermediate and 31.78g of deionized water are metered into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; slowly dropwise adding carbon disulfide (60.8g, 0.8mol) and 40% potassium hydroxide aqueous solution, and controlling the reaction temperature to be 0-25 ℃; controlling the dropping speed of the potassium hydroxide aqueous solution to be higher than that of the carbon disulfide, and controlling the pH value of the reaction solution to be 8-12; after the dropwise addition, the temperature is raised to 40 ℃, the reaction is continued for 4.5 hours, and the temperature is reduced and the material is discharged, so that 318g of orange-red transparent liquid is obtained.
Example 6
The method comprises the following steps: synthesis of polyether cationic intermediate
Adding diethylenetriamine (41.27g, 0.4mol) and a methanol-water solvent (137g, the content of methanol is 35 percent) into a four-neck flask with a thermometer, a reflux condenser and a speed-regulating stirrer; starting stirring, dropwise adding polyepichlorohydrin (32.37g, 0.35mol), and controlling the reaction temperature to be 30-45 ℃; after the polyepichlorohydrin is dripped, the temperature is raised to 50 ℃, the temperature is kept for 1.5h, and the Grignard viscosity is measured and reaches 0.9 second. Then adding 33% trimethylamine (28.66g, 0.16mol), controlling the reaction temperature at 100-105 ℃, and continuing the reaction for 2.5h to obtain the reddish brown transparent water-soluble product.
Step two: synthesis of demulsification and water purification integrated agent
238g of cationic intermediate and 68g of deionized water are metered into a four-neck flask with a thermometer, a reflux condenser and speed-regulating stirring; slowly dropwise adding carbon disulfide (85g, 1.12mol) and 40% sodium hydroxide aqueous solution, and controlling the reaction temperature to be 0-25 ℃; controlling the dropping speed of the alkali liquor to be higher than that of the carbon disulfide, and controlling the pH value of the reaction liquid to be 9-11; after the dropwise addition, the temperature is raised to 35 ℃; the reaction is continued for 4.5h, and the temperature is reduced for discharging to obtain 451g of orange-red transparent liquid.
And (3) reverse demulsification performance evaluation:
the demulsifying and water purifying integrated agent synthesized in the above case is orange red liquid, is mixed and dissolved with water in any proportion, and is added with Fe2+And (4) ion compounding. For the oily wastewater of an offshore oilfield (oil content 19820ppm, turbidity)>10000) The treatment was carried out at a temperature of 60 ℃ with good results, as shown in the following table.
TABLE 1 evaluation of demulsification and water purification integrated agent Performance test results
Claims (4)
1. A synthetic method of a demulsification and water purification integrated agent is characterized by comprising the following steps:
1) synthesis of polyether cationic intermediate
Adding primary amine and an alcohol-water solvent according to the amount, wherein the mass ratio of the alcohol to the water is 1: 1-1: 1.5, and the alcohol-water solvent accounts for 25-45 wt% of the total reaction system; stirring, dropwise adding polyepichlorohydrin, controlling the temperature to be 30-45 ℃, and controlling the reaction molar ratio of primary amine to polyepichlorohydrin to be 1: 0.5-1: 0.7; after the polyepichlorohydrin is dripped, heating to 45-50 ℃, preserving the heat for 1-2h, and measuring the Grignard viscosity to 0.8-1.2 seconds; adding tertiary amine to continue reacting, wherein the reaction molar ratio of the tertiary amine to the primary amine is 0.4: 1-0.65: 1, the reaction temperature is 100-105 ℃, and the reaction time is 2-4h, so as to obtain a reddish brown transparent water-soluble product;
2) synthesis of demulsification and water purification integrated agent
Adding a cationic intermediate and deionized water into a reaction device according to the mass ratio of 3.5:1-6.5: 1; slowly dropwise adding carbon disulfide and alkali liquor, and controlling the reaction temperature to be 0-25 ℃; controlling the dropping speed of the alkali liquor to be higher than that of the carbon disulfide, and controlling the pH =8.5-12 of the reaction liquid; after the dripping is finished, the temperature is raised to 35 to 45 DEGoAnd continuing to react for 3-5h, cooling and discharging to obtain an orange red transparent liquid, wherein the reaction molar ratio of the cationic intermediate to the carbon disulfide is 1: 2.0-1: 3.5.
2. The method for synthesizing the demulsifying and water purifying integral agent as claimed in claim 1, wherein the primary amine is one of diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine and nonaethylenedecamine.
3. The method for synthesizing the demulsifying and water purifying integral agent as claimed in claim 1, wherein the alcohol in the alcohol-water solvent is one of methanol, ethanol and isopropanol.
4. The method for synthesizing the demulsification and water purification integrated agent as claimed in claim 1, wherein the tertiary amine is one of trimethylamine, triethylamine and triethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711394387.3A CN108128877B (en) | 2017-12-21 | 2017-12-21 | Synthetic method of demulsification and water purification integrated agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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