CN111675811A - Amphiphilic allyl polymer for sewage treatment demulsifier and preparation method thereof - Google Patents
Amphiphilic allyl polymer for sewage treatment demulsifier and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an amphiphilic allyl polymer for a sewage treatment demulsifier, a preparation method and a preparation method thereof, belonging to the technical field of sewage treatment in polymer synthesis industry. The amphiphilic allyl polymer for the sewage treatment demulsifier and the preparation method thereof are obtained by carrying out polymerization reaction on a diallyl-terminated polyether and one or more of low-hydrogen silicone oil, Acrylamide (AM), Acrylic Acid (AA) or chloropropene. The amphiphilic allyl polymer for the sewage treatment demulsifier has the characteristics of strong demulsification capability, high demulsification speed, less dosage and lower demulsification temperature, and is particularly suitable for thick oil emulsion; meanwhile, the invention provides a simple and convenient preparation method.
Description
Technical Field
The invention relates to an amphiphilic allyl polymer for a sewage treatment demulsifier, a preparation method and a preparation method thereof, belonging to the technical field of sewage treatment in polymer synthesis industry.
Background
Common sewage treatment agents comprise inorganic sedimentation agents such as aluminum salt, ferric salt and alum, and polymeric flocculants such as cation, anion, nonionic and zwitterionic polyacrylamide and polyaluminium chloride, and can be used as sewage treatment agents in different applications, and amphiphilic allyl polymers are used as demulsifiers and are rarely researched in the field of sewage treatment at present. Inorganic settling agents such as aluminum salt, ferric salt, alum and the like can carry out primary water purification with simpler pollution-causing cause, and polymeric flocculant has obvious and thorough treatment effect in the field of organic industrial sewage treatment compared with the inorganic settling agent, but along with increasingly complex industrial wastewater components, the sewage treatment agent is required to have both hydrophilic performance and excellent oleophylic performance. Aiming at the problem of the limitation of sewage treatment of the existing sewage treatment agent, a novel water treatment agent needs to be developed urgently, an allyl polymer is an amphiphilic block copolymer, an allyl alcohol ether chain segment has hydrophilic water solubility, and a macromolecular compound (containing hydrogen silicone oil, acrylamide, acrylic acid or chloropropene) part has lipophilicity, so that the surface tension of a sewage emulsion is reduced, and the water treatment agent is incomparable with other organic sewage treatment agents. The amphiphilic block copolymer improves the sewage treatment effect of the traditional sewage treatment agent.
For example, the organic silicon surfactant is formed by connecting a polyether chain segment and a polysiloxane chain segment through chemical bonds, the hydrophilic polyether chain segment has good water solubility, the hydrophobic polysiloxane chain segment reduces the surface tension of the emulsion, the emulsion breaking effect is good, and the copolymer also has biocompatibility, good adaptability and low glass transition temperature, which is incomparable with other organic surfactants. Current research on silicone surfactants has focused primarily on grafting hydrophilic organic substituents onto hydrophobic silicone backbones, while few amphiphilic block copolymers have been developed.
The ether end capping means that hydroxyl on the polyether is subjected to etherification or esterification reaction through various organic small molecular compounds, and active hydrogen on the hydroxyl is substituted by various short-chain alkyl, aralkyl or ester groups. After capping, the basic properties of the ether are unchanged, but some new properties are added. Of further interest is the end-capping of the terminal hydroxyl groups of ethers containing double bonds. The general ether containing double bond is used to react with some macromolecular compounds, such as hydrogen-containing silicone oil, acrylamide, acrylic acid or chloropropene, etc. to prepare various polyether modified compounds. The hydrogen-containing silicone oil mainly reacts by the addition reaction of alkenyl on double-bond-containing polyether and macromolecular compounds to generate Si-C bonds, and the generated compounds are not easy to hydrolyze and have good stability. The non-terminated alkenyl polyether inevitably generates Si-O-C bonds due to the existence of hydroxyl, and easily causes crosslinking in the copolymer, so that the product quality is reduced. The hydroxyl groups must therefore be terminated before the reaction to increase the effective content of the copolymer.
Disclosure of Invention
The invention aims to provide an amphiphilic allyl polymer for a sewage treatment demulsifier, and a high-molecular demulsifier prepared from the amphiphilic allyl polymer has the characteristics of strong demulsification capability, high demulsification speed, small dosage, low demulsification temperature and particular suitability for a thick oil emulsion; meanwhile, the invention provides a simple and convenient preparation method.
The amphiphilic allyl polymer for the sewage treatment demulsifier and the preparation method thereof are obtained by carrying out polymerization reaction on a diallyl-terminated polyether and one or more of low-hydrogen silicone oil, Acrylamide (AM), Acrylic Acid (AA) or chloropropene.
The structural formula of the bi-propenyl terminated polyether is as follows:
the diallyl terminated polyether is obtained by taking allyl alcohol as an initiator, carrying out ring-opening polymerization on the allyl alcohol as well as epoxypropane and epoxyethane under the action of a catalyst to obtain allyl alcohol ether, converting the allyl alcohol ether into sodium allyl alcohol ether, and then reacting the allyl alcohol ether with allyl chloride.
The allyl alcohol has a simple molecular structure and contains double bonds, and the allyl alcohol is selected as an initiator raw material of the end-capped polyether, and is reacted with PO and EO under a proper condition by selecting a proper catalyst to generate the allyl alcohol ether. In the invention, the molecular weight is preferably controlled to be 500-600g/mol because the molecular weight cannot be too large in consideration of the steric hindrance and viscosity of the polymerized allyl alcohol ether. Then the hydroxyl is terminated by allyl alcohol to obtain the polymer containing double bond structure.
The catalyst is one or more of potassium propenolate, sodium propenolate, lithium aluminium hydride or boron trifluoride diethyl etherate, and preferably potassium propenolate.
The process for preparing the propylene glycol ether is as follows:
feeding the propylene oxide and the ethylene oxide at the temperature of less than or equal to 40 ℃, controlling the polymerization reaction temperature at 90-95 ℃, carrying out polymerization reaction for 1-3 hours, and then carrying out internal pressure reaction at the temperature of 90-95 ℃ for 1.5-2.5 hours; the internal pressure reaction is pressurized to 0.38MPa, and the pressure is reduced to 0.1MPa along with the reaction.
The preparation process of the sodium propylene alcohol ether comprises the following steps:
reacting propylene alcohol ether with sodium methoxide solution, controlling the temperature at 100-120 ℃, preferably 100 ℃, and vacuumizing to remove methanol in the sodium methoxide solution and methanol generated by the reaction. The temperature of the vacuum pumping is controlled to be 100-110 ℃, the pressure is controlled to be-0.08-0.09 MPa, and the time is 1-3 h. The sodium methoxide solution is a commercially available product, and its concentration is not required.
The preparation process of the diallyl terminated polyether comprises the following steps:
reacting sodium allyl alcohol ether with allyl chloride, heating to 80-90 ℃, keeping the kettle pressure at 0.35-0.40 MPa, reacting for 1-2 h, and removing excessive allyl chloride and volatile components thereof under reduced pressure after the reaction is finished.
Reacting sodium allyl alcohol ether with allyl chloride to obtain diallyl terminated polyether, treating with an adsorbent, and filtering to obtain diallyl terminated polyether; the adsorbent is one or more of magnesium silicate, aluminum silicate, magnesium aluminum silicate or diatomite, preferably magnesium aluminum silicate.
As a preferable technical scheme, the amphiphilic allyl polymer for the sewage treatment demulsifier and the preparation method thereof comprise the following steps:
(1) adding a catalyst into a stainless steel reaction kettle, after nitrogen replacement, sucking propylene alcohol by using a suction pipe, starting stirring, and keeping the temperature to be less than or equal to 30 ℃; heating for dehydration for half an hour at the temperature of 35-40 ℃; adding propylene oxide and ethylene oxide at 35-40 deg.C, and heating to make the polymerization reaction temperature be 90-95 deg.C; then carrying out internal pressure reaction for 20-30min at the temperature of 90-95 ℃; cooling to 50 ℃, adding an adsorbent for post-treatment to obtain allyl alcohol ether with the molecular weight of 500-600 g/mol;
(2) the hydroxyl groups of the polyether are converted to sodium alkoxide groups by addition of sodium methoxide solution:
adding the propylene alcohol ether and the sodium methoxide solution obtained in the step (1) into a rotary film evaporator, controlling the reaction temperature to be 100-120 ℃, vacuumizing to remove methanol in the sodium methoxide solution and methanol generated in the reaction, controlling the vacuumizing temperature to be 100-110 ℃, controlling the pressure to be-0.08-0.09 MPa, and cooling the material to be below 50 ℃ for 1-3 h, and discharging.
(3) Transferring the material in the step (2) to a stainless steel reaction kettle, adding allyl chloride into the kettle, heating to 50-110 ℃, keeping the kettle pressure at 0.35-0.40 MPa, reacting for 1-2 h, removing excessive allyl chloride and volatile components thereof under reduced pressure, cooling to 50 ℃, discharging to obtain a crude product of the diallyl terminated polyether, carrying out post-treatment on the crude product of the diallyl terminated polyether by using an adsorbent, and refining to obtain the diallyl terminated polyether.
(4) The allyl polymer for the water treatment demulsifier is obtained by reacting and polymerizing the diallyl-terminated polyether and macromolecular compounds such as low-hydrogen silicone oil, Acrylamide (AM), Acrylic Acid (AA) and chloropropene according to a certain proportion.
The obtained allyl polymer product for the demulsifier has light color, the molecular weight of 1000g/mol and the viscosity of 800mPa.s, is suitable for demulsification at low temperature (less than 60 ℃), the dosage of the allyl polymer is 100mL/L, the demulsification capability is strong, the demulsification is completed in 10 minutes, sewage is obviously layered, the water quality is clear after filtration, and COD (chemical oxygen demand) is highCrThe removal rate reaches 81 percent, and the removed water is clear, and the COD value is tested to be less than or equal to 15mg/L, thereby reaching the index of the first class and the second class water.
In step (1), propylene oxide and ethylene oxide were fed at a feed rate of 800 g/h.
The preferred 3L of stainless steel reation kettle.
The reaction equation of the step (1) is as follows:
the reaction equation of the step (2) is as follows:
the reaction equation of the step (3) is as follows:
preferably, in the polymerization reaction of acrylamide and diallyl terminated polyether, the monomer concentration is 30-50%, the monomer ratio is (1-2): 0.5-1), the reaction temperature is 40-60 ℃, and the amount of the initiator (when the mass ratio of sodium bisulfite to ammonium peroxydisulfate is 1: 2) is 0.15-0.35%.
Preferably, in the polymerization reaction of acrylic acid and the diallyl-terminated polyether, the monomer ratio is 1:1, the reaction temperature is 75 ℃, and the initiator (in the case that the mass ratio of the sodium bisulfite to the ammonium persulfate is 1: 2) is used in an amount of 1%.
Preferably, in the polymerization reaction of chloropropene and diallyl terminated polyether, the monomer ratio is 1:1, the reaction temperature is 60 ℃, and the amount of the initiator (in the case that the mass ratio of sodium bisulfite to ammonium persulfate is 1: 2) is 0.75%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a synthesis research of a polymer demulsifier for sewage treatment, and the prepared diallyl-terminated polyether has a molecular structure with double bonds at two ends, has high double bond content and improves the effective components of a copolymer;
(2) the diallyl terminated polyether is reacted with certain macromolecular compounds such as low hydrogen silicone oil, Acrylamide (AM), Acrylic Acid (AA) and chloropropene for polymerization to prepare various polyether modified compounds, namely allyl polymers, so that the generated compounds are not easy to hydrolyze and have good stability, and the main reaction in the synthesis of the allyl polymers is the addition reaction of alkenyl on the polyether containing double bonds and the macromolecular compounds to generate amphiphilic block copolymers;
(3) the polymer demulsifier prepared from allyl polymer has strong demulsifying ability (sewage is obviously layered, water quality is clear after filtration, and COD is achieved under the optimal reaction conditionCrThe polymer crude oil demulsifier has the characteristics of high demulsification speed (demulsification and layering are basically completed within 10 minutes), small dosage (the addition amount is less than 100 mL/L), low demulsification temperature (lower than 60 ℃), and particular suitability for sewage treatment in polymer synthesis industry, has clean water after dehydration, can greatly reduce the production cost on the premise that the demulsification effect is not lower than that of a conventional demulsifier, has wide application space in the sewage treatment industry, and has great environmental protection significance;
(4) the preparation method is simple and convenient, and is beneficial to industrial production.
Detailed Description
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to these examples.
Example 1
(1) Adding potassium propenolate into a 3L stainless steel reaction kettle, after the oxygen content is replaced by nitrogen gas, sucking the propenolate by using a suction pipe, starting stirring, and keeping the temperature at 30 ℃; heating for dehydration for half an hour at the temperature of 35 ℃; adding PO and EO at a slow speed at 35 ℃, and gradually raising the temperature to enable the polymerization reaction temperature to be 90 ℃; then carrying out internal pressure reaction for half an hour at the temperature of 90 ℃; cooling to 50 deg.C, sampling and detecting; refining after the product is qualified, and adding an adsorbent for post-treatment to obtain the propylene alcohol ether with the molecular weight of 500 g/mol.
(2) Adding calculated amounts of propylene alcohol ether and sodium methoxide solution into a rotary film evaporator, and controlling the reaction temperature to be 100 +/-3 ℃. Vacuumizing to remove methanol in the sodium methoxide solution and methanol generated in the alcohol exchange reaction, wherein the methanol removing temperature is controlled at 105 +/-3 ℃, the surface pressure is-0.085 MPa, and the time is 1 h. Cooling the material to below 50 ℃ and discharging.
(3) And (4) transferring the material in the step 2 to a 3L stainless steel reaction kettle. Adding allyl chloride into a kettle, heating to 80 ℃, keeping the kettle pressure at 0.38MPa, reacting for about 2 hours, removing excessive allyl chloride and volatile components thereof under reduced pressure, cooling to 50 ℃, and discharging to obtain a crude product of the diallyl terminated polyether. And (3) carrying out post-treatment and refining on the crude polyether product by using an adsorbent magnesium aluminum silicate to obtain the diallyl terminated polyether A.
(4) At 110 ℃, adding a certain amount of diallyl terminated polyether A and a small amount of chloroplatinic acid solution catalyst (the amount of the catalyst is respectively 30 mug/g) dissolved in isopropanol into a four-mouth bottle provided with a thermometer and an electric stirrer, then starting the stirrer to stir and heat, controlling the temperature within a constant temperature range, opening a constant pressure burette to drip a certain amount of low hydrogen silicone oil into the four-mouth bottle, starting timing when the low hydrogen silicone oil is dripped out (the molar ratio of C to Si to H is respectively 1.2:1), and keeping the temperature to react for 10 hours to obtain the polysiloxane.
The obtained organosilicon polymer product for the demulsifier has light color, the molecular weight of 700g/mol, the viscosity of 800mPa.s, is suitable for demulsification at low temperature (50 ℃), the adding amount of the allyl polymer is 100mL/L, the demulsification capability is strong, demulsification is completed in 10 minutes, sewage is obviously layered, the water quality is clear after filtration, and COD (chemical oxygen demand) isCrThe removal rate reaches 79 percent, and the product is removedThe water quality is clear, the COD value is 13mg/L and the COD is less than or equal to 15mg/L through tests, and the index of the first class and the second class water is reached.
Example 2
(1) Adding potassium propenolate into a 3L stainless steel reaction kettle, after the oxygen content is replaced by nitrogen gas, sucking the propenolate by using a suction pipe, starting stirring, and keeping the temperature at 30 ℃; heating for dehydration for half an hour at the temperature of 35 ℃; adding PO and EO at a slow speed at 35 ℃, and gradually raising the temperature to enable the polymerization reaction temperature to be 90 ℃; then carrying out internal pressure reaction for half an hour at the temperature of 90 ℃; cooling to 50 deg.C, sampling and detecting; refining after the product is qualified, and adding an adsorbent for post-treatment to obtain the propylene alcohol ether with the molecular weight of 500 g/mol.
(2) Adding calculated amounts of propylene alcohol ether and sodium methoxide solution into a rotary film evaporator, and controlling the reaction temperature to be 100 +/-3 ℃. Vacuumizing to remove methanol in the sodium methoxide solution and methanol generated in the alcohol exchange reaction, wherein the methanol removing temperature is controlled at 105 +/-3 ℃, the surface pressure is-0.085 MPa, and the time is 1 h. Cooling the material to below 50 ℃ and discharging.
(3) And (4) transferring the material in the step 2 to a 3L stainless steel reaction kettle. Adding allyl chloride into a kettle, heating to 80 ℃, keeping the kettle pressure at 0.38MPa, reacting for about 2 hours, removing excessive allyl chloride and volatile components thereof under reduced pressure, cooling to 50 ℃, and discharging to obtain a crude product of the diallyl terminated polyether. And (3) carrying out post-treatment and refining on the crude polyether product by using an adsorbent magnesium aluminum silicate to obtain the diallyl terminated polyether A.
(4) In the polymerization reaction of acrylamide and the diallyl-terminated polyether A, the monomer concentration is 40%, the monomer ratio is 2:1, the reaction temperature is 50 ℃, and the amount of the initiator (under the condition that the mass ratio of sodium bisulfite to ammonium persulfate is 1: 2) is 0.25%.
The obtained organosilicon polymer product for the demulsifier has light color, molecular weight of 1000g/mol, viscosity of 1000mPa.s, is suitable for demulsification at low temperature (less than 60 ℃), the addition amount of the allyl polymer is 100mL/L, the demulsification capability is strong, demulsification is completed within 8 minutes, sewage is obviously layered, water quality is clear after filtration, and COD (chemical oxygen demand) isCrThe removal rate reaches 75 percent, and the removed water is clear, and the COD value is 11mg/L and less than or equal to 15mg/L through tests, thereby reaching the index of the second class water.
Example 3
(1) Adding sodium allyl alcohol into a 3L stainless steel reaction kettle, sucking in allyl alcohol by using a suction pipe after the oxygen content is replaced by nitrogen gas is qualified, and starting stirring at the temperature of 28 ℃; heating for dehydration for half an hour at 38 ℃; adding PO and EO at a slow speed at 38 ℃, and gradually raising the temperature to ensure that the polymerization temperature is 93 ℃; then carrying out internal pressure reaction for half an hour at the temperature of 93 ℃; cooling to 50 deg.C, sampling and detecting; refining after the product is qualified, and adding an adsorbent for post-treatment to obtain the propylene alcohol ether with the molecular weight of 550 g/mol.
(2) Adding calculated amounts of propylene alcohol ether and sodium methoxide solution into a rotary film evaporator, and controlling the reaction temperature to be 110 +/-3 ℃. Vacuumizing to remove methanol in the sodium methoxide solution and methanol generated in the alcohol exchange reaction, wherein the methanol removing temperature is controlled at 100 +/-3 ℃, the surface pressure is-0.08 MPa, and the time is 2 h. Cooling the material to below 50 ℃ and discharging.
(3) And (4) transferring the material in the step 2 to a 3L stainless steel reaction kettle. Adding allyl chloride into a kettle, heating to 80 ℃, keeping the kettle pressure at 0.40MPa, reacting for about 1h, removing excessive allyl chloride and volatile components thereof under reduced pressure, cooling to 50 ℃, and discharging to obtain a crude product of the diallyl terminated polyether. And (3) carrying out post-treatment and refining on the crude polyether product by using magnesium silicate as an adsorbent to obtain the diallyl terminated polyether B.
(4) In the polymerization reaction of acrylic acid and diallyl-terminated polyether B and the polymerization reaction of alcohol ether, the monomer ratio is 1:1, the reaction temperature is 75 ℃, and the use amount of an initiator (under the condition that the mass ratio of sodium bisulfite to ammonium persulfate is 1: 2) is 1%.
The obtained allyl acrylic polymer used as the demulsifier has light color, molecular weight of 850g/mol, viscosity of 900mPa.s, is suitable for demulsification at low temperature (less than 60 ℃), the adding amount of the allyl acrylic polymer is 80mL/L, the demulsification capability is strong, demulsification is completed in 10 minutes, sewage is obviously layered, water quality is clear after filtration, and COD (chemical oxygen demand) isCrThe removal rate reaches 77 percent, and the removed water is clear, and the COD value is 10mg/L and less than or equal to 15mg/L through tests, thereby reaching the index of the second class water.
Example 4
(1) Adding lithium aluminum hydride into a 3L stainless steel reaction kettle, after the oxygen content is replaced by nitrogen gas, sucking propylene alcohol by using a suction pipe, starting stirring, and keeping the temperature at 25 ℃; heating for dehydration for half an hour at the temperature of 40 ℃; adding PO and EO at a slow speed at 40 ℃, and gradually raising the temperature to ensure that the polymerization reaction temperature is 95 ℃; then carrying out internal pressure reaction for half an hour at the temperature of 95 ℃; cooling to 50 deg.C, sampling and detecting; refining after the product is qualified, and adding an adsorbent for post-treatment to obtain the propylene alcohol ether with the molecular weight of 600 g/mol.
(2) Adding calculated amounts of propylene alcohol ether and sodium methoxide solution into a rotary film evaporator, and controlling the reaction temperature to be 120 +/-3 ℃. Vacuumizing to remove methanol in the sodium methoxide solution and methanol generated in the alcohol exchange reaction, wherein the methanol removing temperature is controlled at 110 +/-3 ℃, the surface pressure is-0.09 MPa, and the time is 1.5 h. Cooling the material to below 50 ℃ and discharging.
(3) And (4) transferring the material in the step 2 to a 3L stainless steel reaction kettle. Adding allyl chloride into a kettle, heating to 80 ℃, keeping the kettle pressure at 0.35MPa, reacting for about 1.5h, removing excessive allyl chloride and volatile components thereof under reduced pressure, cooling to 50 ℃, and discharging to obtain a crude product of the diallyl terminated polyether. And (3) carrying out post-treatment and refining on the crude polyether product by using aluminum silicate as an adsorbent to obtain the diallyl-terminated polyether C.
(4) In the polymerization reaction of chloropropene and diallyl-terminated polyether C and the polymerization reaction of alcohol ether, the monomer ratio is 1:1, the reaction temperature is 60 ℃, and the dosage of an initiator (under the condition that the mass ratio of sodium bisulfite to ammonium persulfate is 1: 2) is 0.75 percent.
The obtained allyl chloropropene polymer used as the demulsifier has light color, the molecular weight of 900g/mol, the viscosity of 900mPa.s, is suitable for demulsification at low temperature (less than 60 ℃), the adding amount of the allyl polymer is 95mL/L, the demulsification capability is strong, demulsification is completed in 10 minutes, sewage is obviously layered, the water quality is clear after filtration, and COD (chemical oxygen demand) isCrThe removal rate reaches 80 percent, and the removed water is clear, and the COD value is 9mg/L and less than or equal to 15mg/L through tests, thereby reaching the index of the second class water.
Comparative example 1
Adding potassium propenolate into a 3L stainless steel reaction kettle, after the oxygen content is replaced by nitrogen gas, sucking the propenolate by using a suction pipe, starting stirring, and keeping the temperature at 30 ℃; heating and dehydrating for half an hour at the temperature of 35 ℃; PO and EO feed at 90 ℃; then carrying out internal pressure reaction for half an hour at the temperature of 90 ℃; cooling to 90 ℃, and sampling and detecting; and (4) refining after the polyether is qualified, and performing post-treatment and refining on the polyether crude product by using adsorbent diatomite to obtain the propylene alcohol ether D.
The performance specifications of the dipropylene-terminated polyether A, B, C and the allyl alcohol ether D prepared in examples 1-3 and comparative example 1 are listed in table 1.
TABLE 1 Performance indices of dipropylene terminated polyether A, B, C and allyl alcohol ether D
Since the hydroxyl groups are terminated by propenyl groups, the product ideally contains no hydroxyl groups, and therefore the quality index also does not have a hydroxyl value. But the incomplete end capping condition exists in the experimental process, and a small amount of hydroxyl value is measured in the index according to the analysis result of the performance index. In addition, the unsaturation value of the double-propenyl product is greatly improved relative to the unsaturation value of the propenyl alcohol ether.
The etherification end capping polyether polyol containing allyl-type propylene alcohol ether can react with macromolecular compounds such as low-hydrogen silicone oil, Acrylamide (AM), Acrylic Acid (AA) and chloropropene to polymerize to obtain allyl polymers because both ends of the etherification end capping polyether polyol contain double bond end capping.
Comparative example 2
(1) Taking the same polymer sewage sample as in example 1-4, adding polyacrylamide as a traditional polymer flocculant, demulsifying at a higher temperature (90 ℃), wherein when the dosage of the polyacrylamide is 100mL/L, the demulsification speed is slow, the sewage is not obviously layered after 30 minutes, the filtered water is slightly turbid, and COD isCrThe removal rate is 53 percent, the tested COD value is 25mg/L, the COD value is less than or equal to 30mg/L, the three water indexes belong to the polluted water quality.
(2) When the dosage of polyacrylamide reaches 500mL/L, demulsification is required at a higher temperature (90 ℃), when the dosage of polyacrylamide is 100mL/L, the demulsification speed is slower, sewage is not obviously layered after 30 minutes, the water quality is slightly turbid after filtration, and COD (chemical oxygen demand) isCrThe removal rate was 67% throughThe COD value is 20mg/L and the COD is less than or equal to 30mg/L, which are three water indexes and belong to polluted water quality.
When the dosage of polyacrylamide reaches 500mL/L and 100mL/L polyferric sulfate is added, demulsification needs to be carried out at a higher temperature (80 ℃), the demulsification speed is slower, sewage is gradually layered after 30 minutes, the water quality is slightly turbid after filtration, and COD (chemical oxygen demand) isCrThe removal rate is 76%, the COD value is 15mg/L and the COD is less than or equal to 15mg/L through tests, and the index of the second class water is reached.
The amphiphilic allyl polymer is used as a demulsifier in the field of sewage treatment, is an amphiphilic block copolymer, has hydrophilic water solubility in an allyl alcohol ether chain segment, has lipophilicity in a macromolecular compound (containing hydrogen silicone oil, acrylamide, acrylic acid or chloropropene) part, reduces the surface tension of sewage emulsion, has better sewage treatment effect compared with the traditional macromolecular flocculant polyacrylamide, has wide application space in the sewage treatment industry, has greater environmental protection significance, and can generate greater economic benefit and social benefit.
Claims (10)
1. An amphiphilic allyl polymer for a sewage treatment demulsifier and a preparation method thereof are characterized in that: the polyether is obtained by polymerization reaction of bipropenyl terminated polyether and one or more of low-hydrogen silicone oil, acrylamide, acrylic acid or chloropropene.
2. The amphiphilic allyl polymer for the sewage treatment demulsifier of claim 1 and the preparation method thereof, wherein the amphiphilic allyl polymer comprises: the structural formula of the diallyl terminated polyether is as follows:
3. the amphiphilic allyl polymer for the sewage treatment demulsifier of claim 1 and the preparation method thereof, wherein the amphiphilic allyl polymer comprises: the diallyl terminated polyether is prepared by taking allyl alcohol as an initiator, carrying out ring-opening polymerization on the allyl alcohol as well as epoxypropane and epoxyethane under the action of a catalyst to obtain allyl alcohol ether, converting the allyl alcohol ether into sodium allyl alcohol ether, and then reacting the allyl alcohol ether with allyl chloride.
4. The amphiphilic allyl polymer for the sewage treatment demulsifier of claim 3 and the preparation method thereof, wherein the amphiphilic allyl polymer comprises: the molecular weight of the propylene alcohol ether is 500-600 g/mol.
5. The amphiphilic allyl polymer for the sewage treatment demulsifier of claim 3 and the preparation method thereof, wherein the amphiphilic allyl polymer comprises: the catalyst is one or more of potassium acrylate alkoxide, sodium acrylate alkoxide, lithium aluminum hydride or boron trifluoride diethyl etherate.
6. An amphiphilic allyl polymer for a sewage treatment demulsifier according to any one of claims 1 to 5 and a method for preparing the same, wherein the amphiphilic allyl polymer comprises: the method comprises the following steps:
(1) adding a catalyst into a reaction kettle, sucking propylene alcohol by using a suction pipe after nitrogen replacement, adding epoxypropane and ethylene oxide after stirring for polymerization reaction, cooling to 45-65 ℃, adding an adsorbent for post-treatment to obtain propylene alcohol ether;
(2) adding the propylene alcohol ether and sodium methoxide solution obtained in the step (1) into a thin film evaporator for reaction, then carrying out vacuum pumping treatment, cooling the material to below 50 ℃, and discharging;
(3) transferring the material in the step (2) to a reaction kettle, adding allyl chloride into the reaction kettle for reaction, removing excessive allyl chloride and volatile components thereof under reduced pressure, cooling to 50 ℃, discharging, and obtaining a crude product of the diallyl terminated polyether;
(4) carrying out post-treatment on the crude product of the diallyl terminated polyether by using an adsorbent, and refining to obtain the diallyl terminated polyether;
(5) the allyl polymer for the water treatment demulsifier is obtained by reacting and polymerizing the diallyl-terminated polyether and the macromolecular compound according to a certain proportion.
7. The amphiphilic allyl polymer for the sewage treatment demulsifier of claim 6 and the preparation method thereof, wherein the amphiphilic allyl polymer for the sewage treatment demulsifier comprises: in the step (1), the stirring temperature is less than or equal to 30 ℃, and the temperature is 35-40 ℃ during temperature rise dehydration.
8. The amphiphilic allyl polymer for the sewage treatment demulsifier of claim 6 and the preparation method thereof, wherein the amphiphilic allyl polymer for the sewage treatment demulsifier comprises: in the step (1), the temperature of the polymerization reaction is 90-95 ℃, and the reaction time is 20-30 min.
9. The amphiphilic allyl polymer for the sewage treatment demulsifier of claim 6 and the preparation method thereof, wherein the amphiphilic allyl polymer for the sewage treatment demulsifier comprises: in the step (2), the reaction temperature is 100-120 ℃.
10. The amphiphilic allyl polymer for the sewage treatment demulsifier of claim 6 and the preparation method thereof, wherein the amphiphilic allyl polymer for the sewage treatment demulsifier comprises: in the step (3), the reaction temperature is 50-110 ℃, the pressure is 0.35-0.40 MPa, and the reaction time is 1-2 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112430284A (en) * | 2020-11-18 | 2021-03-02 | 威海翔泽新材料科技有限公司 | Demulsifier for mary oil and synthetic method thereof |
| CN113563539A (en) * | 2021-07-21 | 2021-10-29 | 中国石油大学(华东) | Water-based drilling fluid surface hydration inhibitor and preparation method and application thereof |
| CN115261004A (en) * | 2022-09-27 | 2022-11-01 | 胜利油田凯渡石油技术开发有限公司 | Thick oil viscosity reducer and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112430284A (en) * | 2020-11-18 | 2021-03-02 | 威海翔泽新材料科技有限公司 | Demulsifier for mary oil and synthetic method thereof |
| CN112430284B (en) * | 2020-11-18 | 2022-05-31 | 威海翔泽新材料科技有限公司 | Demulsifier for mary oil and synthetic method thereof |
| CN113563539A (en) * | 2021-07-21 | 2021-10-29 | 中国石油大学(华东) | Water-based drilling fluid surface hydration inhibitor and preparation method and application thereof |
| CN113563539B (en) * | 2021-07-21 | 2024-02-23 | 中国石油大学(华东) | Water-based drilling fluid surface hydration inhibitor and preparation method and application thereof |
| CN115261004A (en) * | 2022-09-27 | 2022-11-01 | 胜利油田凯渡石油技术开发有限公司 | Thick oil viscosity reducer and preparation method thereof |
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