CN114478901B - Cationic polymer containing hydrophobic group, preparation method thereof, demulsifier and application thereof - Google Patents
Cationic polymer containing hydrophobic group, preparation method thereof, demulsifier and application thereof Download PDFInfo
- Publication number
- CN114478901B CN114478901B CN202011160737.1A CN202011160737A CN114478901B CN 114478901 B CN114478901 B CN 114478901B CN 202011160737 A CN202011160737 A CN 202011160737A CN 114478901 B CN114478901 B CN 114478901B
- Authority
- CN
- China
- Prior art keywords
- cationic polymer
- groups
- structural unit
- weight
- cationic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920006317 cationic polymer Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000001165 hydrophobic group Chemical group 0.000 title claims abstract description 11
- 239000010865 sewage Substances 0.000 claims abstract description 24
- 239000010779 crude oil Substances 0.000 claims abstract description 18
- 125000002091 cationic group Chemical group 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 15
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 11
- -1 azo compound Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 230000033116 oxidation-reduction process Effects 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 239000000693 micelle Substances 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229940001474 sodium thiosulfate Drugs 0.000 claims description 2
- 229950004959 sorbitan oleate Drugs 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a cationic polymer containing hydrophobic groups, a preparation method thereof, a demulsifier thereof and application thereof. The cationic polymer contains at least one of a structural unit M shown in a formula (1), a structural unit N shown in a formula (2), a structural unit X shown in a formula (3) and a structural unit Y shown in a formula (4),
Description
Technical Field
The invention relates to the field of demulsifiers, in particular to a cationic polymer containing hydrophobic groups, a preparation method thereof, a demulsifier and application thereof.
Background
The O/W emulsion interface of the oil field is generally electronegative, so the cationic reverse demulsifier is a demulsifier which has relatively rapid development in recent years. The emulsion drops mutually collide and coalesce to demulsify by neutralizing the negative charge of an oil-water interface, compressing to destroy an electric double layer and weakening the strength of an interface film. And the polymer chain segments generate bridging and flocculation effects to form oil beads with the particle size reaching the preset particle size, and the oil beads are gradually separated from water under the buoyancy effect of the water, so that the purpose of reverse emulsion breaking is achieved. In addition, if the hydrophobic group is introduced into the cationic surfactant, the flocculation demulsification effect can be remarkably improved through the association with hydrophobic organic matters in the oily sewage.
With the implementation of yield increasing means such as tertiary oil recovery, the properties of oil extraction sewage in the oil field are greatly changed, and the oil extraction sewage has the characteristics of high viscosity, high emulsion stability of oil drops in water and suspended matters and the like, and the difficulty of oil and water separation is increased; and the oil content in the raw water is higher than that of the conventional produced water.
The increase of the difficulty of the sewage treatment of the produced liquid requires the development of a corresponding novel efficient water treatment agent. Polyacrylamide is a common polymeric flocculant in China, and the raw material monomer acrylamide can be carcinogenic, has high price and is limited in application.
Disclosure of Invention
In order to solve the problems in the prior art, the invention adopts at least one of nontoxic cationic monomers such as methacryloxyethyl trimethyl ammonium chloride (DMC), acryloxyethyl trimethyl ammonium chloride (DAC) and dimethyl diallyl ammonium chloride (DMDAAC) and biological base material dibutyl itaconate as comonomers to synthesize the environment-friendly cationic polymer containing hydrophobic groups.
It is an object of the present invention to provide a cationic polymer containing a hydrophobic group, comprising at least one of a structural unit M represented by the formula (1), a structural unit N represented by the formula (2), a structural unit X represented by the formula (3), and a structural unit Y represented by the formula (4),
in the cationic polymer, the total of the structural unit M, the structural unit N and the structural unit X accounts for 85-95% of the weight of the cationic polymer; the structural unit Y accounts for 5-15% of the weight of the cationic polymer.
Preferably, the sum of the structural units M, N and X accounts for 88-92% of the weight of the cationic polymer; the structural unit Y accounts for 8-12% of the weight of the cationic polymer.
The cationic polymer of the present invention may contain one, two or three of the structural unit M represented by the formula (1), the structural unit N represented by the formula (2) and the structural unit X represented by the formula (3).
The second object of the invention is to provide a preparation method of the cationic polymer containing hydrophobic groups, which comprises the step of carrying out aqueous solution free radical micelle polymerization on components including dibutyl itaconate, cationic monomers and chain extenders.
The cationic monomer is selected from one, two or three of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride.
The cationic polymer is polymerized by dibutyl itaconate and at least one cationic monomer selected from methacryloxyethyl trimethyl ammonium chloride (DMC), acryloxyethyl trimethyl ammonium chloride (DAC) and dimethyl diallyl ammonium chloride (DMDAAC).
Based on the technical scheme, the weight part of the dibutyl itaconate is 5-15 parts, preferably 8-12 parts;
the total weight parts of the methacryloxyethyl trimethyl ammonium chloride (DMC), the acryloxyethyl trimethyl ammonium chloride (DAC), and the dimethyldiallyl ammonium chloride (DMDAAC) are 85 to 95 parts, preferably 88 to 92 parts.
Based on the technical scheme, the chain extender is a compound with double bonds at two ends, preferably at least one of N, N-methylene bisacrylamide, ethylene glycol diacrylate and polyethylene glycol diacrylate;
the weight portion of the chain extender is 0.1 to 0.8 portion, preferably 0.2 to 0.5 portion, based on 100 portions of the total weight of the dibutyl itaconate and the cationic monomer.
Preferably, the preparation method of the invention comprises the following steps:
step 1, mixing components including dibutyl itaconate, cationic monomers and a surfactant with a solvent;
and 2, adding a chain extender and an initiator to form a reaction system solution in inert atmosphere, and carrying out polymerization reaction to obtain the cationic polymer.
On the basis of the technical scheme, the surfactant can be various conventional surfactants, and is preferably cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alkylphenol ethoxylate (OP-10), sorbitan oleate (Span-80) and the like;
based on 100 parts of the total weight of dibutyl itaconate and cationic monomers, the weight part of the surfactant is 2-5 parts, preferably 2-3 parts.
Based on the technical scheme, the chain extender is a compound with double bonds at two ends, preferably N, N-methylene bisacrylamide, ethylene glycol diacrylate, polyethylene glycol diacrylate (the molecular weight is preferably 200, 400 and 600) and the like;
the weight portion of the chain extender is 0.1 to 1 portion, preferably 0.1 to 0.8 portion, based on 100 portions of the total weight of the dibutyl itaconate and the cationic monomer.
Based on the technical proposal, the initiator is an oxidation-reduction system or a water-soluble azo compound system or a mixture of the two,
wherein the oxidation-reduction system comprises an oxidation-reduction system composed of at least one of potassium persulfate, ammonium persulfate, hydrogen peroxide and the like and at least one of sodium thiosulfate, ferrous chloride, ascorbic acid and the like;
the water-soluble azo compound system component comprises 2,2 ’ -dimethyl azodiisobutyrate, 2 ’ -azo [2- (2-imidazolinyl) propane]At least one of dihydrochloride, azobisisobutylamidine hydrochloride, azo (2-amidinopropane) dihydride, and the like.
The initiator is 0.2 to 1.5 parts by weight, preferably 0.5 to 1.0 parts by weight, based on 100 parts by weight of the total weight of dibutyl itaconate and the cationic monomer.
On the basis of the technical scheme, the solvent is deionized water, and the solid content is 20-50% (weight percentage) by adding the deionized water.
Based on the technical scheme, in the step 2, the solid content of the reaction system solution is 20-50wt%, preferably 30-40wt%;
in the step 2, the reaction temperature is 30-50 ℃, preferably 40-45 ℃;
in the step 2, the reaction time is not less than 4 hours.
On the basis of the technical scheme, the steps of precipitation, drying and the like can be carried out after the step 2 to obtain polymer solids, or the polymer solids can be directly discharged as polymer solution products.
The polymer solutions of the present invention are pale yellow to pale red in appearance.
According to a preferred embodiment of the invention, the preparation method comprises the following steps:
step 1, dibutyl itaconate, at least one selected from methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride, a surfactant and a solvent are added into a reactor, and the mixture is fully stirred until the mixture is completely dissolved.
And 2, replacing air in the reactor by nitrogen, continuously introducing nitrogen, heating to raise the temperature, and adding a chain extender and an initiator to start reaction at 30-50 ℃ for at least 4h.
Step 3, cooling, precipitating with absolute ethyl alcohol or acetone, and drying to obtain pale yellow to pale red solid; or directly discharging the solution product to obtain the cationic polymer aqueous solution.
The cationic polymer is prepared from dibutyl itaconate and at least one cationic monomer selected from methacryloxyethyl trimethyl ammonium chloride (DMC), acryloxyethyl trimethyl ammonium chloride (DAC) and dimethyl diallyl ammonium chloride (DMDAAC) by a conventional free radical micelle polymerization method, and a redox initiation system, an azo initiation system or a composite initiation system is used; in addition, the chain extender is added, so that a network branched structure can be prepared, and the obtained reverse demulsifier has a good demulsification and deoiling effect on crude oil sewage.
The invention further provides application of the cationic polymer or the cationic polymer obtained by the preparation method in crude oil sewage treatment.
The environment-friendly cationic polymer containing hydrophobic groups and containing bio-based raw materials can be used as a reverse demulsifier for treating oily sewage of oil fields.
The cationic polymer provided by the invention can treat crude oil sewage with various oil contents. The oily wastewater may be of various sources, for example, oilfield wastewater, daily chemical wastewater, and the like.
The invention also provides a reverse demulsifier comprising the cationic polymer or the cationic polymer obtained by the preparation method.
The reverse demulsifier may be an aqueous solution containing the above cationic polymer, a solution product obtained by the above cationic polymer production method, or an aqueous solution of a solid product obtained by the above cationic polymer production method.
The cationic polymers of the present invention may be used in the form of solutions when used to treat crude oil-in-water emulsions. The concentration of the solution may preferably be 0.2 to 30% by weight.
The cationic polymer can be used as the reverse demulsifier, and can also be used as one of the components of the reverse demulsifier to be matched with other demulsifiers in the prior art so as to improve the broad-spectrum performance of the reverse demulsifier.
The other demulsifiers in the prior art can be, for example, cationic surfactants prepared by reacting epichlorohydrin with polyamine, dithiocarbamates, diallyl dimethyl ammonium chloride homopolymers, cationic polyacrylamides and the like.
The reverse demulsifier can be prepared from cationic polymers with different proportions according to different original oil sewage, and can also be compounded with other reverse demulsifiers or flocculating agents to improve the broad-spectrum performance of the reverse demulsifier.
The fifth object of the present invention is to provide a method for treating crude oil sewage, which comprises contacting crude oil sewage with the reverse demulsifier described above. Wherein the reverse demulsifier contains the cationic polymer.
The amount of the reverse demulsifier may be the same as or different from the prior art, and preferably, the amount of the cationic polymer in the reverse demulsifier is 1 to 200mg, more preferably 20 to 100mg, relative to 1L of crude oil sewage.
According to the treatment method of the invention, the contact temperature is 40-60 ℃, preferably 50-55 ℃; the contact time is 0.5 to 4 hours, preferably 1 to 3 hours.
The crude oil sewage may be of various sources, for example, oilfield sewage, daily chemical sewage, etc.
The beneficial effects of the invention are as follows:
the invention relates to a cationic polymer containing hydrophobic groups and a preparation method thereof, wherein the cationic polymer is prepared from dibutyl itaconate and at least one cationic monomer selected from methacryloxyethyl trimethyl ammonium chloride (DMC), acryloxyethyl trimethyl ammonium chloride (DAC) and dimethyl diallyl ammonium chloride (DMDAAC) by a conventional aqueous solution free radical micelle polymerization method, and a redox initiation system, an azo initiation system or a composite initiation system is used. The chain extender is introduced in the polymerization process, so that the branching degree of the polymer is improved, the surface activity of the reverse demulsifier is enhanced, and the prepared cationic polymer has good demulsification and deoiling performances on crude oil sewage.
In addition, itaconic acid is an important class of bio-based chemical base stock. The wide application of the polymer formed by the itaconic acid and the derivative thereof can effectively solve the problems caused by the exhaustion of petroleum resources and environmental pollution, and has very important significance.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the specific embodiment of the present invention are commercially available.
Example 1
The operation steps are as follows:
step 1, weighing 5 g of dibutyl itaconate, 1 g of hexadecyl trimethyl ammonium bromide, 20 g of methacryloxyethyl trimethyl ammonium chloride, 20 g of acryloxyethyl trimethyl ammonium chloride, 5 g of dimethyl diallyl ammonium chloride and 100 g of deionized water, adding the materials into a reactor, and fully stirring until the materials are completely dissolved.
Step 2, replacing air in the reactor by nitrogen, continuously introducing nitrogen, heating to 30 ℃, adding 0.05 g of N, N-methylene bisacrylamide, 0.159 g of sodium thiosulfate and potassium persulfate (the weight ratio of the two is 1:2), and starting the reaction. The reaction was carried out for a total of 6 hours at 30 ℃.
And 3, cooling, precipitating with absolute ethyl alcohol, and drying to obtain a light red solid.
Example 2
Step 1, 1 g of dibutyl itaconate, 0.6 g of sodium dodecyl sulfate, 19 g of methacryloyloxyethyl trimethyl ammonium chloride and 30 g of deionized water are weighed into a reactor and stirred sufficiently until completely dissolved.
Step 2, replacing air in the reactor with nitrogen, continuously introducing nitrogen, heating to 40 ℃, adding 0.06 g of ethylene glycol diacrylate and 0.16 g of azo (2-amidinopropane) dihydride to start the reaction. The reaction was carried out at 42℃for 4h.
And 3, cooling, precipitating with acetone, and drying to obtain pale yellow solid.
Example 3
Step 1, 3.6 g of dibutyl itaconate, 0.9 g of shan pear sugar alcohol anhydride oleate, 15 g of acryloyloxyethyl trimethyl ammonium chloride, 11.4 g of dimethyl diallyl ammonium chloride and 120 g of deionized water are weighed into a reactor, and are fully stirred until the materials are completely dissolved.
Step 2, replacing air in the reactor by nitrogen, continuously introducing nitrogen, heating to 30 ℃, adding 0.2 g of polyethylene glycol diacrylate (molecular weight 200) and 0.28 g of sodium thiosulfate, potassium persulfate and azo (2-amidinopropane) dihydride (the weight ratio of the three is 1:2:1), and starting the reaction. After 4 hours of reaction, the reaction temperature was raised to 50℃and the reaction was continued for 2 hours.
And 3, cooling to obtain a light red polymer solution product.
Comparative example 1
The cationic polymer was prepared according to the method of ZL201310183542.2 example 1.
The method comprises the following specific steps:
(1) 2.56 g of butyl acrylate, 1.62 g of cetyltrimethylammonium bromide, 78.7 g of methacryloyloxyethyl trimethylammonium chloride and 244 g of deionized water were weighed into a reactor and stirred well until completely dissolved.
(2) The air in the reactor was replaced with nitrogen and continuously purged with nitrogen, heated to 35℃and 0.163 g of sodium thiosulfate and potassium persulfate (1:2 by weight) were added to start the reaction. The reaction was maintained at 35℃for 6h.
(3) Cooling, precipitating with absolute ethanol, and drying to obtain white solid.
Application example 1
The polymers of examples 1 to 3 and comparative example 1 and SF-Y001 type cationic polyacrylamide manufactured by Wen county tetragonal water treatment materials Co., ltd. Having a good effect on the market at present were used as reverse demulsifiers in the amounts shown in Table 1, and aqueous solutions having a concentration of 1.5% by weight were prepared.
The above 3 reverse demulsifier aqueous solutions were reacted with crude oil sewage (oil content: 1000mg/l, polymer content: 100 mg/l) of a estuary oil recovery plant at 50℃for 0.5 hours, the oil-water interface after the contact was observed according to the SY/T5797-93 method, then oil-water separation was performed, the oil content in the obtained aqueous phase was measured according to the SY/T5797-93 method, and the appearance of the aqueous phase was observed, and the results are shown in Table 1 below.
TABLE 1
From the test results, the example 1 and the example 3 have better demulsification and deoiling effects on the crude oil sewage of the Cheng Dong combined station, and are obviously superior to those of the cationic polyacrylamide and the comparative example 1.
Claims (15)
1. A hydrophobic group-containing cationic polymer comprising at least one of a structural unit M represented by the formula (1), a structural unit N represented by the formula (2), a structural unit X represented by the formula (3), and a structural unit Y represented by the formula (4),
wherein the sum of the structural unit M, the structural unit N and the structural unit X accounts for 85-95% of the weight of the cationic polymer; the structural unit Y accounts for 5-15% of the weight of the cationic polymer.
2. The cationic polymer of claim 1, wherein:
the sum of the structural unit M, the structural unit N and the structural unit X accounts for 88-92% of the weight of the cationic polymer; the structural unit Y accounts for 8-12% of the weight of the cationic polymer.
3. A process for the preparation of a cationic polymer according to claim 1 or 2, comprising the steps of: and performing aqueous solution free radical micelle polymerization on components comprising dibutyl itaconate, a cationic monomer and a chain extender, wherein the cationic monomer is at least one selected from methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride.
4. A process for the preparation of a cationic polymer according to claim 3, characterized in that:
the weight part of the dibutyl itaconate is 5-15 parts; the total weight of the cationic monomer is 85-95 parts; and/or the number of the groups of groups,
the chain extender is a compound with double bonds at two ends; and/or the number of the groups of groups,
the weight portion of the chain extender is 0.1-1 portion.
5. The method for producing a cationic polymer according to claim 4, wherein:
the chain extender is at least one of N, N-methylene bisacrylamide, ethylene glycol diacrylate and polyethylene glycol diacrylate; and/or the number of the groups of groups,
the weight portion of the chain extender is 0.1 to 0.8 portion.
6. The method for producing a cationic polymer according to claim 3 or 4, characterized by comprising the steps of:
step 1, mixing components including dibutyl itaconate, cationic monomers and a surfactant with a solvent;
and 2, adding a chain extender and an initiator to form a reaction system solution in inert atmosphere, and carrying out polymerization reaction to obtain the cationic polymer.
7. The method for producing a cationic polymer according to claim 6, wherein:
the surfactant is at least one selected from cetyltrimethylammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alkylphenol ethoxylates and sorbitan oleate; and/or the number of the groups of groups,
the weight part of the surfactant is 2-5 parts; and/or the number of the groups of groups,
the initiator is an oxidation-reduction system and/or a water-soluble azo compound system; and/or the number of the groups of groups,
the weight portion of the initiator is 0.2 to 1.5 portions.
8. The method for producing a cationic polymer according to claim 7, wherein:
the weight part of the surfactant is 2-3 parts; and/or the number of the groups of groups,
the oxidation-reduction system comprises at least one of potassium persulfate, ammonium persulfate and hydrogen peroxide and at least one of sodium thiosulfate, ferrous chloride and ascorbic acid; the water-soluble azo compound is selected from 2,2 ’ -dimethyl azodiisobutyrate, 2 ’ -azo [2- (2-imidazolinyl) propane]At least one of dihydrochloride, azobisisobutylamidine hydrochloride, azo (2-amidinopropane) dihydride; and/or the number of the groups of groups,
the weight portion of the initiator is 0.5 to 1.0 portion.
9. The method for producing a cationic polymer according to claim 6, wherein:
in the step 2, the solid content of the reaction system solution is 20-50wt%; and/or the number of the groups of groups,
the reaction temperature is 30-50 ℃; and/or the number of the groups of groups,
the reaction time is not less than 4 hours.
10. The method for producing a cationic polymer according to claim 9, characterized in that:
the solid content of the reaction system solution is 20-40 wt%; and/or the number of the groups of groups,
the reaction temperature is 40-45 ℃.
11. Use of a cationic polymer according to claim 1 or 2 or a cationic polymer obtained by the process according to any one of claims 3 to 10 in the treatment of crude oil sewage.
12. A reverse demulsifier comprising the cationic polymer according to claim 1 or 2 or the cationic polymer obtainable by the process according to any one of claims 3 to 10.
13. A method of treating crude oil sewage comprising contacting the crude oil sewage with the reverse demulsifier according to claim 12.
14. The method for treating crude oil wastewater according to claim 13, wherein:
the contact temperature is 40-60 ℃, and the contact time is 0.5-4 hours; and/or the number of the groups of groups,
the cationic polymer is used in the demulsifier in an amount of 1-200 mg relative to 1L of crude oil sewage.
15. The method for treating crude oil wastewater according to claim 14, wherein:
the cationic polymer is used in the demulsifier in an amount of 20-100 mg relative to 1L of crude oil sewage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011160737.1A CN114478901B (en) | 2020-10-27 | 2020-10-27 | Cationic polymer containing hydrophobic group, preparation method thereof, demulsifier and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011160737.1A CN114478901B (en) | 2020-10-27 | 2020-10-27 | Cationic polymer containing hydrophobic group, preparation method thereof, demulsifier and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114478901A CN114478901A (en) | 2022-05-13 |
| CN114478901B true CN114478901B (en) | 2023-07-21 |
Family
ID=81471560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011160737.1A Active CN114478901B (en) | 2020-10-27 | 2020-10-27 | Cationic polymer containing hydrophobic group, preparation method thereof, demulsifier and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114478901B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1179363A (en) * | 1956-05-29 | 1959-05-22 | Rohm & Haas | Process for the production of polymer structures containing ion exchange groups |
| AU2013214125A1 (en) * | 2012-02-03 | 2014-07-31 | Dsm Ip Assets B.V. | Polymer, process and composition |
| CN105217841A (en) * | 2015-11-01 | 2016-01-06 | 刘应才 | Method for producing pure water from coking wastewater |
| CN105601808A (en) * | 2015-07-14 | 2016-05-25 | 孟红琳 | Preparing method of modified polyacrylamide with good stability |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2824124A1 (en) * | 2013-07-12 | 2015-01-14 | Basf Se | Polymeric dispersing agent |
-
2020
- 2020-10-27 CN CN202011160737.1A patent/CN114478901B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1179363A (en) * | 1956-05-29 | 1959-05-22 | Rohm & Haas | Process for the production of polymer structures containing ion exchange groups |
| AU2013214125A1 (en) * | 2012-02-03 | 2014-07-31 | Dsm Ip Assets B.V. | Polymer, process and composition |
| CN105601808A (en) * | 2015-07-14 | 2016-05-25 | 孟红琳 | Preparing method of modified polyacrylamide with good stability |
| CN105217841A (en) * | 2015-11-01 | 2016-01-06 | 刘应才 | Method for producing pure water from coking wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114478901A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6323306B1 (en) | Preparation of water-soluble cross-linked cationic polymers | |
| CN106866881B (en) | hydrophobic association acrylamide polymer emulsion and preparation method thereof | |
| US4831092A (en) | Micellar process for preparing hydrophobically functionalized cationic polymers (C-2114) | |
| EP0624603A2 (en) | High molecular weight acrylamide polymers, method of making and use of same | |
| Zhou et al. | Hydrophobic modification of cationic microblocked polyacrylamide and its enhanced flocculation performance for oily wastewater treatment | |
| EP0172723A2 (en) | Water soluble polymers | |
| CN101260174A (en) | A kind of cationic hydrophobic association polymer and its preparation method and application | |
| KR20050084682A (en) | Modified polymeric flocculants with improved performance characteristics | |
| CN100489001C (en) | Water-soluble copolymer, high polymer flocculant and method of dehydrating sludge | |
| CN111057577B (en) | Acrylate copolymer and preparation method thereof, water-in-oil emulsion demulsifier and application thereof | |
| CN114262412A (en) | Anti-shearing modified polyacrylamide and application thereof | |
| CN102029124B (en) | Polyacrylamide surfactant and preparation method thereof | |
| CN116425920A (en) | Metallocene modified polyacrylamide and preparation method thereof | |
| CN114478901B (en) | Cationic polymer containing hydrophobic group, preparation method thereof, demulsifier and application thereof | |
| US5650465A (en) | Ampholytic polymers and polymeric microemulsions | |
| JP4018473B2 (en) | Crosslinkable ionic water-soluble polymer composed of powder | |
| CN114426632B (en) | Amphoteric polyelectrolyte, preparation method thereof, polymeric flocculant and oily sewage treatment method | |
| CN117720684A (en) | Amphoteric polymer and preparation method and application thereof | |
| CN112876629B (en) | Oil displacement agent, and synthesis method and application thereof | |
| EP0669349B1 (en) | Ampholytic polymers, polymeric microemulsions, methods of producing same, and use of same as flocculant | |
| CN113831480B (en) | Bio-based amphoteric polymer and preparation method and application thereof | |
| CN114539470B (en) | Acrylamide functional polymer and preparation method and application thereof | |
| CN113831479B (en) | Lignin-based amphoteric polymer containing ultra-long chain structure and preparation method and application thereof | |
| Zhang et al. | Preparation of a novel flocculant and its performance for treating acidic oily wastewater | |
| CN117510715B (en) | Multifunctional amphiphilic polymer water treatment agent suitable for beneficiation wastewater treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |