CN117735655A - Stone oil sewage treatment agent and preparation method thereof - Google Patents
Stone oil sewage treatment agent and preparation method thereof Download PDFInfo
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- CN117735655A CN117735655A CN202410187197.8A CN202410187197A CN117735655A CN 117735655 A CN117735655 A CN 117735655A CN 202410187197 A CN202410187197 A CN 202410187197A CN 117735655 A CN117735655 A CN 117735655A
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- 239000010865 sewage Substances 0.000 title claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004575 stone Substances 0.000 title description 2
- 239000003208 petroleum Substances 0.000 claims abstract description 59
- 239000011259 mixed solution Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229920006318 anionic polymer Polymers 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 8
- 229920000053 polysorbate 80 Polymers 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 7
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 238000012688 inverse emulsion polymerization Methods 0.000 claims description 3
- 238000005956 quaternization reaction Methods 0.000 claims description 3
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical class CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BGHCVCJVXZWKCC-NJFSPNSNSA-N tetradecane Chemical class CCCCCCCCCCCCC[14CH3] BGHCVCJVXZWKCC-NJFSPNSNSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 239000007822 coupling agent Substances 0.000 claims 1
- 238000007720 emulsion polymerization reaction Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000003980 solgel method Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 15
- 230000033558 biomineral tissue development Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 salt ions Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to the field of sewage treatment, in particular to a petroleum sewage treatment agent and a preparation method thereof.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a petroleum sewage treatment agent and a preparation method thereof.
Background
Petroleum is one of the main subjects of geological exploration, a viscous, dark brown liquid, known as "industrial blood". The upper part of the crust has petroleum storage, and the main component of petroleum is a mixture of various alkanes, cycloalkanes and aromatic hydrocarbons. Petroleum wastewater is generally wastewater discharged from petrochemical plants, organic matters contained in the petroleum wastewater are mainly hydrocarbons and derivatives thereof, organic pollution is serious, chemical Oxygen Demand (COD), solid suspended matters (SS), petroleum and total phosphorus are high, and many reactions of petrochemical production are completed under the action of catalysts, so that the petroleum wastewater often contains heavy metals, and at present, physical, chemical and biological treatment methods are generally adopted for the treatment of the petroleum wastewater.
Patent technical document CN112939166a discloses a flocculant for treating petroleum refining delayed coking oily sewage, which is used for demulsification treatment of coking oily sewage by using the demulsification oil removal flocculant to reduce the oil content, COD and suspended matters of the sewage, however, the method has low efficiency and unsatisfactory treatment effect, and especially for some petroleum sewage containing complex organic components and heavy metals.
The patent technical document CN113716634A discloses a preparation method of a medicament for treating petrochemical oily sewage, which solves the problem of poor treatment effect of products such as the prior sewage treatment medicament (polyaluminum oxide, polyferric sulfate, aluminum sulfate) and the like by the medicament containing aluminum hydroxide, sulfuric acid, a catalyst and montmorillonite stock solution, and reduces the problem of difficult operation of later biochemical load, but the method needs to use a strong oxidant or flocculant, and can effectively remove certain pollutants, but can introduce new pollution or produce secondary pollution.
Disclosure of Invention
In view of the above, the invention aims to provide a petroleum sewage treatment agent and a preparation method thereof, so as to solve the problem of low oil yield of the petroleum sewage treatment agent in the prior art.
Based on the above purpose, the invention provides a petroleum sewage treatment agent and a preparation method thereof.
The preparation method of the petroleum sewage treatment agent comprises the following steps:
s1, adoptingSol-gel method of SiO 2 The shell layer is wrapped around the ferroferric oxide inner core to obtain a magnetic carrier;
s2, modifying the magnetic carrier by adopting a vinyl silane coupling agent to obtain an alkenylation magnetic carrier;
s3, adopting two-step inverse emulsion polymerization, wherein the first step is to graft a chain-shaped anionic polymer on the surface of the alkenyl magnetic carrier, and the second step is to graft a branched amino polymer at the tail end of the anionic polymer, so as to obtain a double-layer coated magnetic carrier;
s4, quaternizing amino groups in the double-layer coated magnetic carrier by adopting chloralkane to obtain an oil sewage treatment agent;
the chain-shaped anionic polymer in the step S3 is a copolymer of acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid;
the branched aminopolymer in step S3 is a copolymer of dimethylaminopropyl methacrylamide, N' -methylenebisacrylamide and triallylamine.
Preferably, the average particle size of the ferroferric oxide in the step S1 is 50-100nm, and the preparation method of the magnetic carrier in the step S1 is as follows:
s11, dispersing ferroferric oxide in secondary water by ultrasonic to obtain a mixed solution A, and dispersing tetraethyl orthosilicate in methanol by ultrasonic to obtain a mixed solution B;
s12, mixing the mixed solution A and the mixed solution B, stirring for 15min, adding ammonia water, stirring for 15min by ultrasound, and stirring for 3.5-5h to obtain a mixed solution C;
s13, washing the mixed solution C to be neutral after magnetic separation, soaking the mixed solution C in hydrochloric acid with the pH value of 1 for 24 hours, washing the mixed solution C to be neutral, and drying the mixed solution C in a drying oven to obtain a magnetic carrier;
the dosage ratio of the ferroferric oxide, the secondary water, the tetraethyl orthosilicate and the methanol in the step S11 is 1.5-2.5g:35-45mL:1.7-1.8mL:70-90mL;
in the step S12, the volume ratio of the mixed solution A to the mixed solution B to the ammonia water is 40-45:80-85:3-5.
Preferably, the vinyl silane coupling agent in the step S2 is one of vinyl trimethoxy silane, vinyl triethoxy silane and vinyl tri (β -methoxyethoxy) silane;
the preparation method of the alkenylation magnetic carrier in the step S2 comprises the following steps:
adding a magnetic carrier into a mixed solution of ethanol and water, adding a vinyl silane coupling agent, adjusting the pH to 4-5, then reacting for 6-8 hours at 65-70 ℃, washing, and separating to obtain an alkenylation magnetic carrier;
the dosage ratio of the magnetic carrier, the ethanol, the water and the vinyl silane coupling agent is 1.5-2.5g:250-350mL:80-120mL:1.5-2.5g.
Preferably, the specific steps of the two-step inverse emulsion polymerization in step S3 are:
s31, mixing n-hexane, tween-80 and n-amyl alcohol to obtain an oil phase;
s32, mixing acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and deionized water to obtain a water phase A;
s33, mixing dimethylaminopropyl methacrylamide, N' -methylenebisacrylamide, triallylamine and deionized water to obtain a water phase B;
s34, adding the alkenylation magnetic carrier into the oil phase under the nitrogen atmosphere to obtain a dispersion liquid, adding the water phase A, ammonium persulfate and sodium bisulphite into the dispersion liquid, carrying out polymerization reaction for 5-6h at 35-45 ℃, adding the water phase B, and carrying out polymerization reaction for 2-3h at 35-45 ℃ to obtain the double-layer coated magnetic carrier.
Preferably, in step S31, the mass ratio of n-hexane, tween-80 and n-amyl alcohol is 14-18:6-10:4-7.
Preferably, in step S32, the mass ratio of the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid and the deionized water is 12-15g:13-16g:90-110mL.
Preferably, the mass ratio of the dimethylaminopropyl methacrylamide, the N, N' -methylenebisacrylamide, the triallylamine and the deionized water in the step S33 is 10-12g:11-13g:10-12g:90-120mL.
Preferably, in step S34, the mass ratio of the alkenylated magnetic carrier, oil phase, aqueous phase a, ammonium persulfate, sodium bisulphite, and aqueous phase B is 18-22:8-12:3-5:7-9:1-2:3-5.
Preferably, the mass ratio of the chlorinated alkane to the double-layer coated magnetic carrier in the step S4 is 30-36:2932, the quaternization reaction temperature in the step S4 is 60-70 ℃, the reaction time is 10-14h, and the chlorinated alkane in the step S4 is any one of chlorinated decane, chlorinated dodecane and chlorinated tetradecane.
A petroleum sewage treatment agent obtained according to the method for preparing a petroleum sewage treatment agent according to any one of the above.
The invention has the beneficial effects that:
the oil-sewage treatment agent provided by the invention is obtained by grafting the alkenyl magnetic carrier with the chain-shaped anionic polymer and the branched amino polymer in sequence and then amination, wherein the chain-shaped anionic polymer in the interior expands after water absorption, so that the branched amino polymer grafted by the chain segment can be spread more comfortably, the oil-sewage treatment agent has larger specific surface area, and the oil-sewage treatment agent can be contacted with the oil-sewage more fully, and further the oil removal rate of the oil-sewage and the removal rate of suspended matters are improved.
The branched amino polymer in the petroleum sewage treatment agent provided by the invention is rich in cations on the surface after being subjected to quaternization, and the internal anionic polymer can adsorb the cations in petroleum sewage, so that the cations in the petroleum sewage can migrate to the inside, the influence of a large amount of salt ions in the petroleum sewage on the performance of the petroleum sewage treatment agent is reduced, and finally the demulsification-flocculation capacity of the petroleum sewage treatment agent is improved, so that the oil removal rate and the suspended matter removal rate of the petroleum sewage treatment agent are improved, and in particular, the oil removal rate and the suspended matter removal rate of petroleum sewage with high mineralization rate are improved.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1: the preparation method of the petroleum sewage treatment agent comprises the following steps:
s1, ultrasonically dispersing 1.5g of ferroferric oxide with the average particle size of 50nm in 35mL of secondary water to obtain a mixed solution A, and ultrasonically dispersing 1.7mL of tetraethyl orthosilicate in 70mL of methanol to obtain a mixed solution B;
s2, mixing 40mL of the mixed solution A with 80mL of the mixed solution B, stirring for 15min, adding 3mL of ammonia water, stirring for 15min by ultrasound, and stirring for 3.5h to obtain a mixed solution C;
s3, washing the mixed solution C to be neutral after magnetic separation, soaking the mixed solution C in hydrochloric acid with the pH value of 1 for 24 hours, washing the mixed solution C to be neutral, and drying the mixed solution C in a drying oven to obtain a magnetic carrier;
s4, adding 1.5g of magnetic carrier into a mixed solution of 250mL of ethanol and 80mL of water, adding 1.5g of vinyl trimethoxy silane, adjusting pH to 4, then reacting for 6 hours at 65 ℃, washing, and separating to obtain an alkenylation magnetic carrier;
s5, mixing 14g of n-hexane, 6g of tween-80 and 4g of n-amyl alcohol to obtain an oil phase;
s6, mixing 12g of acrylic acid, 13g of 2-acrylamide-2-methylpropanesulfonic acid and 90mL of deionized water to obtain a water phase A;
s7, mixing 10g of dimethylaminopropyl methacrylamide, 11g of N, N' -methylenebisacrylamide, 10g of triallylamine and 90mL of deionized water to obtain a water phase B;
s8, under the nitrogen atmosphere, 18g of an alkenyl magnetic carrier is added into 8g of an oil phase to obtain a dispersion liquid, 3g of a water phase A, 7g of ammonium persulfate and 1g of sodium bisulphite are added into the dispersion liquid to carry out polymerization reaction for 5 hours at 35 ℃, then 3g of a water phase B is added to carry out polymerization reaction for 2 hours at 35 ℃ to obtain a double-layer wrapped magnetic carrier;
s9, reacting 30g of chlorodecane with 29g of double-layer coated magnetic carrier at 60 ℃ for 10h to obtain the oil sewage treatment agent.
Example 2: the preparation method of the petroleum sewage treatment agent comprises the following steps:
s1, dispersing 2g of ferroferric oxide with the average particle size of 70nm in 40mL of secondary water by ultrasonic, so as to obtain a mixed solution A, and dispersing 1.73mL of tetraethyl orthosilicate in 77mL of methanol by ultrasonic, so as to obtain a mixed solution B;
s2, mixing 42mL of the mixed solution A with 82mL of the mixed solution B, stirring for 15min, adding 4mL of ammonia water, stirring for 15min by ultrasound, and stirring for reaction for 4h to obtain a mixed solution C;
s3, washing the mixed solution C to be neutral after magnetic separation, soaking the mixed solution C in hydrochloric acid with the pH value of 1 for 24 hours, washing the mixed solution C to be neutral, and drying the mixed solution C in a drying oven to obtain a magnetic carrier;
s4, adding 2g of magnetic carrier into a mixed solution of 300mL of ethanol and 90mL of water, adding 2g of vinyltriethoxysilane, adjusting pH to 4.5, then reacting at 67 ℃ for 6.5h, washing, and separating to obtain an alkenylation magnetic carrier;
s5, mixing 16g of n-hexane, 8g of tween-80 and 5g of n-amyl alcohol to obtain an oil phase;
s6, mixing 13g of acrylic acid, 14g of 2-acrylamide-2-methylpropanesulfonic acid and 100mL of deionized water to obtain a water phase A;
s7, mixing 11g of dimethylaminopropyl methacrylamide, 12g of N, N' -methylenebisacrylamide, 11g of triallylamine and 100mL of deionized water to obtain a water phase B;
s8, under the nitrogen atmosphere, 19g of an alkenyl magnetic carrier is added into 10g of an oil phase to obtain a dispersion liquid, then 4g of a water phase A, 8g of ammonium persulfate and 1.5g of sodium bisulfite are added into the dispersion liquid to carry out polymerization reaction for 5.4 hours at 38 ℃, then 3.8g of a water phase B is added to carry out polymerization reaction for 2.3 hours at 38 ℃ to obtain a double-layer coated magnetic carrier;
s9, reacting 32g of chlorododecane with 30g of double-layer coated magnetic carrier at 63 ℃ for 12 hours to obtain the oil sewage treatment agent.
Example 3: the preparation method of the petroleum sewage treatment agent comprises the following steps:
s1, dispersing 2.25g of ferroferric oxide with the average particle size of 90nm in 42.5mL of secondary water by ultrasonic to obtain a mixed solution A, and dispersing 1.76mL of tetraethyl orthosilicate in 84mL of methanol by ultrasonic to obtain a mixed solution B;
s2, mixing 44mL of the mixed solution A and 84mL of the mixed solution B, stirring for 15min, then adding 4.5mL of ammonia water, stirring for 15min by ultrasound, and stirring for 4.5h to obtain a mixed solution C;
s3, washing the mixed solution C to be neutral after magnetic separation, soaking the mixed solution C in hydrochloric acid with the pH value of 1 for 24 hours, washing the mixed solution C to be neutral, and drying the mixed solution C in a drying oven to obtain a magnetic carrier;
s4, adding 2.25g of magnetic carrier into a mixed solution of 325mL of ethanol and 110mL of water, adding 2.25g of vinyl tri (beta-methoxyethoxy) silane, adjusting the pH to 4.5, then reacting for 7h at 68 ℃, washing, and separating to obtain an alkenylation magnetic carrier;
s5, mixing 17g of n-hexane, 9g of tween-80 and 6g of n-amyl alcohol to obtain an oil phase;
s6, mixing 14g of acrylic acid, 15g of 2-acrylamide-2-methylpropanesulfonic acid and 105mL of deionized water to obtain a water phase A;
s7, mixing 11.5g of dimethylaminopropyl methacrylamide, 12.5g of N, N' -methylenebisacrylamide, 11.5g of triallylamine and 110mL of deionized water to obtain a water phase B;
s8, under the nitrogen atmosphere, adding 20g of an alkenyl magnetic carrier into 11g of an oil phase to obtain a dispersion liquid, adding 4.5g of a water phase A, 8.5g of ammonium persulfate and 1.8g of sodium bisulphite into the dispersion liquid, carrying out polymerization reaction for 5.8 hours at 42 ℃, adding 4.4g of a water phase B, and carrying out polymerization reaction for 2.6 hours at 42 ℃ to obtain a double-layer coated magnetic carrier;
s9, reacting 34g of chlorotetradecane with 31g of double-layer coated magnetic carrier at 66 ℃ for 13 hours to obtain the petroleum sewage treatment agent.
Example 4: the preparation method of the petroleum sewage treatment agent comprises the following steps:
s1, dispersing 2.5g of ferroferric oxide with the average particle size of 100nm in 45mL of secondary water by ultrasonic, so as to obtain a mixed solution A, and dispersing 1.8mL of tetraethyl orthosilicate in 90mL of methanol by ultrasonic, so as to obtain a mixed solution B;
s2, mixing 45mL of the mixed solution A with 85mL of the mixed solution B, stirring for 15min, adding 5mL of ammonia water, stirring for 15min by ultrasound, and stirring for reaction for 5h to obtain a mixed solution C;
s3, washing the mixed solution C to be neutral after magnetic separation, soaking the mixed solution C in hydrochloric acid with the pH value of 1 for 24 hours, washing the mixed solution C to be neutral, and drying the mixed solution C in a drying oven to obtain a magnetic carrier;
s4, adding 2.5g of magnetic carrier into a mixed solution of 350mL of ethanol and 120mL of water, adding 2.5g of vinyl tri (beta-methoxyethoxy) silane, adjusting the pH to 5, then reacting at 70 ℃ for 8 hours, washing and separating to obtain an alkenylation magnetic carrier;
s5, mixing 18g of n-hexane, 10g of tween-80 and 7g of n-amyl alcohol to obtain an oil phase;
s6, mixing 15g of acrylic acid, 16g of 2-acrylamide-2-methylpropanesulfonic acid and 110mL of deionized water to obtain a water phase A;
s7, mixing 12g of dimethylaminopropyl methacrylamide, 13g of N, N' -methylenebisacrylamide, 12g of triallylamine and 120mL of deionized water to obtain a water phase B;
s8, adding 22g of an alkenyl magnetic carrier into 12g of an oil phase in a nitrogen atmosphere to obtain a dispersion liquid, adding 5g of a water phase A, 9g of ammonium persulfate and 2g of sodium bisulphite into the dispersion liquid, carrying out polymerization reaction for 6 hours at 45 ℃, adding 5g of a water phase B, and carrying out polymerization reaction for 3 hours at 45 ℃ to obtain a double-layer coated magnetic carrier;
s9, reacting 36g of chlorotetradecane with 32g of double-layer coated magnetic carrier at 70 ℃ for 14h to obtain the petroleum sewage treatment agent.
Comparative example 1:
compared with the example 1, the comparative example has no amino polymer with the tail end grafted and branched on the magnetic carrier of the surface grafted with the anionic polymer in the preparation process of the petroleum sewage treatment agent, other steps and parameters are the same, and the comparative example is not repeated, so that the petroleum sewage treatment agent is finally obtained.
Comparative example 2:
compared with the example 1, the comparative example does not graft chain-shaped anionic polymer on the surface of the alkenyl magnetic carrier in the preparation process of the petroleum sewage treatment agent, but directly grafts branched amino polymer on the surface of the alkenyl magnetic carrier, and the other steps and parameters are the same, so that the comparative example is not repeated, and the petroleum sewage treatment agent is finally obtained.
Comparative example 3:
compared with the example 1, the comparative example does not quaternize the amino groups in the double-layer coated magnetic carrier in the preparation process of the petroleum sewage treatment agent, and the other steps and parameters are the same, so that the petroleum sewage treatment agent is finally obtained without repeated description.
Comparative example 4:
in this example, compared with example 1, only the branched aminopolymer is replaced by the chain aminopolymer, and the other steps and parameters are the same, so that the comparative example is not repeated, and finally the petroleum sewage treatment agent is obtained.
Comparative example 5:
compared with the embodiment 1, the comparative example only replaces the petroleum sewage treatment agent with the magnetic carrier, and the rest steps and parameters are the same, so that the comparative example does not repeat the detailed description, and finally the petroleum sewage treatment agent is obtained.
Performance testing
Mechanical properties:
9 groups of oil field well site sample liquids with 100mL mineralization degree of 3000-8000mg/L are placed into a constant-temperature water bath to be heated to 50 ℃, 10g of petroleum sewage treatment agent prepared in examples 1-4 and comparative examples 1-5 are respectively added into the 9 groups of sample liquids after 30min, oil removal experiments are carried out, and the oil removal rate C of each group of samples is recorded 1 Removal rate C of suspended matter 2 And recording the water quality condition;
9 groups of oil field well site sample liquids with 100mL mineralization degree of 10000mg/L are placed into a constant-temperature water bath to be heated to 50 ℃, 10g of petroleum sewage treatment agents prepared in examples 1-4 and comparative examples 1-5 are respectively added into the 9 groups of sample liquids after 30min, oil removal experiments are carried out, and the oil removal rate C of each group of samples is recorded 3 Removal rate C of suspended matter 4 And the water quality was recorded, and the results are shown in the following table 1:
TABLE 1
Data analysis:
as can be seen from Table 1, the oil-removing rate of the oil-removing sewage treatment agent prepared in the invention is higher for the oil-removing sewage and the suspended matters in the oil-removing sewage, especially the oil-removing rate for the oil-removing sewage with high mineralization degree and the suspended matters therein are obvious.
Compared with example 1, in which the amino polymer having no terminal graft branching was carried out on the magnetic carrier having the surface grafted with the anionic polymer, in example 3, since the amino group in the double-layered coated magnetic carrier was not quaternized and in example 5, the magnetic carrier was directly used as the petroleum sewage treatment agent, which resulted in that the surface of the finally produced petroleum sewage treatment agent was free of cations, the emulsion breaking-flocculation ability was extremely limited, and thus the oil removal rate and removal rate for suspended matters were low, whereas in example 2, the amino polymer was directly grafted and quaternized due to the fact that the alkenyl magnetic carrier was not grafted with the anionic polymer, which affected the degree of contact of the petroleum sewage treatment agent with the petroleum sewage, and in addition, in the case of the petroleum sewage with high mineralization, since the internal anions were not attracted cations in the petroleum sewage, the oil removal rate and removal rate for the suspended matters were greatly reduced, whereas in example 5, the branched amino polymer was merely replaced with chain-like amino polymer, which resulted in less cationic oil removal rate and lower removal rate for the petroleum sewage treatment agent surface.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the invention is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the petroleum sewage treatment agent is characterized by comprising the following steps of:
s1, adopting a sol-gel method to carry out SiO (silicon dioxide) preparation 2 The shell layer is wrapped around the ferroferric oxide inner core to obtain a magnetic carrier;
s2, modifying the magnetic carrier by adopting a vinyl silane coupling agent to obtain an alkenylation magnetic carrier;
s3, adopting two-step inverse emulsion polymerization, wherein the first step is to graft a chain-shaped anionic polymer on the surface of the alkenyl magnetic carrier, and the second step is to graft a branched amino polymer at the tail end of the anionic polymer, so as to obtain a double-layer coated magnetic carrier;
s4, quaternizing amino groups in the double-layer coated magnetic carrier by adopting chloralkane to obtain a petroleum sewage treatment agent;
the chain-shaped anionic polymer in the step S3 is a copolymer of acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid;
the branched aminopolymer in step S3 is a copolymer of dimethylaminopropyl methacrylamide, N' -methylenebisacrylamide and triallylamine.
2. The method for preparing a sewage treatment agent for petroleum according to claim 1, wherein the average particle size of the ferroferric oxide in the step S1 is 50-100nm, and the method for preparing the magnetic carrier in the step S1 is as follows:
s11, dispersing ferroferric oxide in secondary water by ultrasonic to obtain a mixed solution A, and dispersing tetraethyl orthosilicate in methanol by ultrasonic to obtain a mixed solution B;
s12, mixing the mixed solution A and the mixed solution B, stirring for 15min, adding ammonia water, stirring for 15min by ultrasound, and stirring for 3.5-5h to obtain a mixed solution C;
s13, washing the mixed solution C to be neutral after magnetic separation, soaking the mixed solution C in hydrochloric acid with the pH value of 1 for 24 hours, washing the mixed solution C to be neutral, and drying the mixed solution C in a drying oven to obtain a magnetic carrier;
the dosage ratio of the ferroferric oxide, the secondary water, the tetraethyl orthosilicate and the methanol in the step S11 is 1.5-2.5g:35-45mL:1.7-1.8mL:70-90mL;
in the step S12, the volume ratio of the mixed solution A to the mixed solution B to the ammonia water is 40-45:80-85:3-5.
3. The method for preparing a sewage treatment agent for petroleum according to claim 1, wherein the vinylsilane coupling agent in step S2 is one of vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (β -methoxyethoxy) silane;
the preparation method of the alkenylation magnetic carrier in the step S2 comprises the following steps:
adding a magnetic carrier into a mixed solution of ethanol and water, adding a vinyl silane coupling agent, adjusting the pH to 4-5, then reacting for 6-8 hours at 65-70 ℃, washing, and separating to obtain an alkenylation magnetic carrier;
the dosage ratio of the magnetic carrier, the ethanol, the water and the vinyl silane coupling agent is 1.5-2.5g:250-350mL:80-120mL:1.5-2.5g.
4. The method for preparing a sewage treatment agent according to claim 1, wherein the specific steps of the two-step reverse emulsion polymerization in step S3 are as follows:
s31, mixing n-hexane, tween-80 and n-amyl alcohol to obtain an oil phase;
s32, mixing acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and deionized water to obtain a water phase A;
s33, mixing dimethylaminopropyl methacrylamide, N' -methylenebisacrylamide, triallylamine and deionized water to obtain a water phase B;
s34, adding the alkenylation magnetic carrier into the oil phase under the nitrogen atmosphere to obtain a dispersion liquid, adding the water phase A, ammonium persulfate and sodium bisulphite into the dispersion liquid, carrying out polymerization reaction for 5-6h at 35-45 ℃, adding the water phase B, and carrying out polymerization reaction for 2-3h at 35-45 ℃ to obtain the double-layer coated magnetic carrier.
5. The method for preparing a sewage treatment agent according to claim 4, wherein the mass ratio of n-hexane, tween-80 and n-amyl alcohol in step S31 is 14-18:6-10:4-7.
6. The method for preparing a sewage treatment agent for petroleum according to claim 4, wherein the mass ratio of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and deionized water in the step S32 is 12-15g:13-16g:90-110mL.
7. The method for preparing a sewage treatment agent for petroleum according to claim 4, wherein the mass ratio of dimethylaminopropyl methacrylamide, N' -methylenebisacrylamide, triallylamine and deionized water in the step S33 is 10-12g:11-13g:10-12g:90-120mL.
8. The method for preparing a petroleum sewage treatment agent according to claim 4, wherein in the step S34, the mass ratio of the alkenylated magnetic carrier, the oil phase, the water phase a, the ammonium persulfate, the sodium bisulphite and the water phase B is 18-22:8-12:3-5:7-9:1-2:3-5.
9. The preparation method of the petroleum sewage treatment agent according to claim 1, wherein the mass ratio of the chlorinated alkane to the double-layer coated magnetic carrier in the step S4 is 30-36:2932, the quaternization reaction temperature in the step S4 is 60-70 ℃ and the reaction time is 10-14h, and the chlorinated alkane in the step S4 is any one of chlorinated decane, chlorinated dodecane and chlorinated tetradecane.
10. A petroleum sewage treatment agent characterized by being obtained by the method for preparing a petroleum sewage treatment agent according to any one of claims 1 to 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2294098A2 (en) * | 2008-06-27 | 2011-03-16 | Construction Research & Technology GmbH | Time-delayed super-absorbent polymers |
| CN103553181A (en) * | 2013-10-31 | 2014-02-05 | 东南大学 | Preparation method of magnetic antiphase demulsifier |
| CN103980406A (en) * | 2014-05-16 | 2014-08-13 | 苏州大学 | Method for preparing anionic polyacrylamide |
| CN104987474A (en) * | 2015-07-13 | 2015-10-21 | 中国科学院新疆理化技术研究所 | Preparation method of magnetic desalting agent for reducing degree of mineralization of oilfield sewage |
| CN106219669A (en) * | 2016-08-01 | 2016-12-14 | 山东交通学院 | A kind of preparation method of magnetic oxygenated Graphene demulsifier |
| CN113354049A (en) * | 2021-07-12 | 2021-09-07 | 东北石油大学 | Preparation method of hyperbranched magnetic demulsifying flocculant for oil field water treatment |
-
2024
- 2024-02-20 CN CN202410187197.8A patent/CN117735655A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2294098A2 (en) * | 2008-06-27 | 2011-03-16 | Construction Research & Technology GmbH | Time-delayed super-absorbent polymers |
| CN103553181A (en) * | 2013-10-31 | 2014-02-05 | 东南大学 | Preparation method of magnetic antiphase demulsifier |
| CN103980406A (en) * | 2014-05-16 | 2014-08-13 | 苏州大学 | Method for preparing anionic polyacrylamide |
| CN104987474A (en) * | 2015-07-13 | 2015-10-21 | 中国科学院新疆理化技术研究所 | Preparation method of magnetic desalting agent for reducing degree of mineralization of oilfield sewage |
| CN106219669A (en) * | 2016-08-01 | 2016-12-14 | 山东交通学院 | A kind of preparation method of magnetic oxygenated Graphene demulsifier |
| CN113354049A (en) * | 2021-07-12 | 2021-09-07 | 东北石油大学 | Preparation method of hyperbranched magnetic demulsifying flocculant for oil field water treatment |
Non-Patent Citations (2)
| Title |
|---|
| ZHENG, XINYU: "Enhanced adsorption of Orange G from aqueous solutions by quaternary ammonium group-rich magnetic nanoparticles", COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS, no. 580, 5 November 2019 (2019-11-05), pages 123746 * |
| 孔丝纺;文秀芳;皮丕辉;程江;杨卓如;: "磁性微球的制备及其在水处理中的应用", 应用化工, no. 05, 28 May 2007 (2007-05-28) * |
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