CN112852475B - 含氟破乳复合物及油田用破乳剂 - Google Patents
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 34
- 239000011737 fluorine Substances 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 12
- -1 perfluoroalkyl compound Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims description 2
- BKCUGMAGOAPJRG-UHFFFAOYSA-N 4-(nitromethyl)phenol Chemical compound OC1=CC=C(C[N+]([O-])=O)C=C1 BKCUGMAGOAPJRG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- SCWLIHXXYXFUFV-UHFFFAOYSA-M sodium;2,2,3,3,3-pentafluoropropanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)F SCWLIHXXYXFUFV-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- YSHHTXWLHYSYJP-UHFFFAOYSA-M sodium;2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)F YSHHTXWLHYSYJP-UHFFFAOYSA-M 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/097—Preparation of carboxylic acids or their salts, halides or anhydrides from or via nitro-substituted organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于油田破乳领域,具体涉及一种含氟破乳复合物及油田用破乳剂,包括下述质量份组分:全氟羧酸盐1.5‑5份,含氟聚醚羧酸盐1.2‑8份,脂肪醇3.2‑20份,水45‑90份;其中,所述的全氟羧酸盐为RfCOOM2,含氟聚醚羧酸盐CF3CF2CF2O(CF(CF3)CF2O)nCFHCF2O‑C6H6‑COOM1,其中,Rf为C2‑C4的全氟烷基化合物;n为0‑5的整数,M1、M2为Na+,K+,Cs+,NH4 +中的一种。含氟破乳剂具有优良的界面活性,加入含氟破乳剂能够作用于油水界面,明显降低油水界面张力,促进破乳效果。
Description
技术领域
本发明属于油田破乳领域,具体涉及一种含氟破乳复合物及油田用破乳剂。
背景技术
含氟表面活性剂能够一定程度上通过改变原油的流动性,提高原油的开采效率,某些含氟的表面活性剂在石油工业中也可用作破乳剂,石油中加入的破乳剂,吸附到油水形成的乳状液的界面上,促进乳状液破乳,原油会与水分形成乳状液。为达到油水的分离,可以选择加入界面活性高,破坏界面能力强的含氟破乳剂。
发明内容
本发明的目的在于提供一种含氟破乳复合物及油田用破乳剂。
为实现上述目的,本发明采用的技术方案为:
一种含氟破乳复合物,包括下述质量份组分:全氟羧酸盐1.5-5份,含氟聚醚羧酸盐1.2-8份,脂肪醇3.2-20份,水45-90份;其中,所述的全氟羧酸盐为RfCOOM2,含氟聚醚羧酸盐为CF3CF2CF2O(CF(CF3)CF2O)nCFHCF2O-C6H6-COOM1,其中,Rf为C2-C4的全氟烷基化合物;n为1-5的整数,M1、M2为Na+,K+,Cs+,NH4 +中的一种。
所述的脂肪醇为甲醇,乙醇,乙二醇,或者丙三醇中的一种。
具体的,所述的含氟聚醚羧酸盐采用下述方式制备:
1)将全氟乙烯基醚加入溶有对羟基硝基甲基苯和叔丁醇钾的DMF溶液中,搅拌过夜,然后倒入盐酸水溶液中,通过乙醚萃取,硫酸镁干燥,过滤,蒸馏得到中间体(I):
2)所得产物(I)在50~150℃、酸性水溶液中,催化剂作用下转化为中间体(Ⅱ);
3)向所得含氟聚醚羧酸中加入碱性水溶液即得含氟聚醚羧酸盐(I I I);
其中,n为0-5的整数,M1、为Na+,K+,Cs+,NH4 +中的一种。
本发明还包括一种油田用破乳剂,包括所述的含氟破乳复合物、聚合氯化铝溶液以及聚丙烯酰胺溶液。
具体的,含氟破乳复合物、聚合氯化铝溶液以及聚丙烯酰胺溶液的质量比为1:1:2000;聚合氯化铝溶液的浓度为1wt%;聚丙烯酰胺溶液为0.5wt%。
与现有技术相比,本发明的有益效果是:
含氟破乳剂具有优良的界面活性,加入含氟破乳剂能够作用于油水界面,明显降低油水界面张力,促进破乳效果。使用含氟破乳剂能够达到比传统的破乳剂更好的破乳效果,具有使用量少、脱水速率快、脱水程度高等特点。氟表面活性剂应用其高稳定性、抗盐耐碱等性能,使其能够在严苛开采条件下,仍然具有良好的适用性。
具体实施方式
为了使本技术领域的技术人员更好地理解本发明的技术方案,下面结合最佳实施例对本发明作进一步的详细说明。
实施例1:含氟聚醚羧酸盐的制备:包括下述步骤:(1)在室温下,将8.64g全氟丙基乙烯基醚加入溶有6.42g对羟基硝基甲基苯和0.45g叔丁醇钾的DMF溶液中,DMF的体积为50mL,搅拌过夜,然后向其中倒入30mL浓度为1mol/L的盐酸水溶液,之后通过乙醚萃取,硫酸镁干燥,过滤,蒸馏得到中间体(I):
(2)取中间体(Ⅰ)3.69g溶于水中,向其中加入醋酸1.5g,TBAI 0.2g于耐压反应釜内搅拌至完全溶解,将反应釜升温至80℃,在搅拌条件下持续反应24小时,待反应釜降至室温后缓慢打开放液阀,将反应釜内液体转移至精馏塔釜,精馏得到中间体(Ⅱ):
取1.5g中间体(II)溶于10g水中,搅拌条件下向其中缓慢滴加1mol/LNaOH水溶液4.5mL,继续搅拌0.5小时,将液体转移至旋转蒸发仪蒸馏瓶中,通过旋转蒸发得到干燥固体粉末产物含氟聚醚羧酸钠:
实施例2:将全氟丙酸钠1.5g,含氟聚醚羧酸钠CF3CF2CF2OCFHCF2OC6H6COONa(实施例1得到的产物III)1.2g溶于45克水中,常温搅拌至完全溶解,向其中加入乙醇3.2g混匀即可得到含氟表面活性剂复合物。1g上述含氟表面活性剂复合物、1g浓度为1%的聚合氯化铝溶液与2000g浓度为0.5%的聚丙烯酰胺溶液在常温下进行搅拌均匀混合即可得到油田用含氟破乳剂。
实施例3:全氟乙酸钠盐3g,含氟聚醚羧酸钾CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCFHCF2OC6H6COOK(制备方法同实施例1中含氟聚醚羧酸盐的制备)2g溶于90g水中,常温搅拌至完全溶解,向其中加入乙醇5g混匀即可得到含氟表面活性剂复合物;1g上述含氟表面活性剂复合物、1g浓度为1%的聚合氯化铝溶液与2000g浓度为0.5%的聚丙烯酰胺溶液在常温下进行搅拌均匀混合即可得到油田用含氟破乳剂。
实施例4:全氟丁酸钠5g,含氟聚醚羧酸钠CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCFHCF2OC6H6COONa 8g,(制备方法同实施例1中含氟聚醚羧酸盐的制备),溶于90g水中,常温搅拌至完全溶解,向其中加入乙醇20g混匀即可得到含氟表面活性剂复合物。1g上述含氟表面活性剂复合物、1g浓度为1%的聚合氯化铝溶液与2000g浓度为0.5%的聚丙烯酰胺溶液在常温下进行搅拌均匀混合即可得到油田用含氟破乳剂。
表1
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (1)
1.一种油田用含氟破乳剂的制备方法,其特征在于,采用下述方式:
将全氟丙酸钠1.5g,含氟聚醚羧酸钠CF3CF2CF2OCFHCF2OC6H6COONa 1.2g溶于45克水中,常温搅拌至完全溶解,向其中加入乙醇3.2g混匀即可得到含氟表面活性剂复合物;
1g上述含氟表面活性剂复合物、1g浓度为1%的聚合氯化铝溶液与2000g浓度为0.5%的聚丙烯酰胺溶液在常温下进行搅拌均匀混合即可得到油田用含氟破乳剂;
其中,所述的CF3CF2CF2OCFHCF2OC6H6COONa采用下述方式制备:
(1)在室温下,将8.64g全氟丙基乙烯基醚加入溶有6.42g对羟基硝基甲基苯和0.45g叔丁醇钾的DMF溶液中,DMF的体积为50mL,搅拌过夜,然后向其中倒入30mL浓度为1mol/L的盐酸水溶液,之后通过乙醚萃取,硫酸镁干燥,过滤,蒸馏得到中间体(I);
(2)取中间体(Ⅰ)3.69g溶于水中,向其中加入醋酸1.5g,TBAI 0.2g于耐压反应釜内搅拌至完全溶解,将反应釜升温至80℃,在搅拌条件下持续反应24小时,待反应釜降至室温后缓慢打开放液阀,将反应釜内液体转移至精馏塔釜,精馏得到中间体(Ⅱ);
取1.5g中间体(II)溶于10g水中,搅拌条件下向其中缓慢滴加1mol/L KOH水溶液4.5mL,继续搅拌0.5小时,将液体转移至旋转蒸发仪蒸馏瓶中,通过旋转蒸发得到干燥固体粉末产物含氟聚醚羧酸钠(III);
(III)。
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Citations (5)
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