CN1305563A - 在石油抽提中防止结垢的方法 - Google Patents
在石油抽提中防止结垢的方法 Download PDFInfo
- Publication number
- CN1305563A CN1305563A CN99807192.7A CN99807192A CN1305563A CN 1305563 A CN1305563 A CN 1305563A CN 99807192 A CN99807192 A CN 99807192A CN 1305563 A CN1305563 A CN 1305563A
- Authority
- CN
- China
- Prior art keywords
- levulan
- carboxyl
- described method
- oil
- scale preventative
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000000605 extraction Methods 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 3
- 159000000008 strontium salts Chemical class 0.000 claims abstract 2
- 229940118199 levulan Drugs 0.000 claims description 28
- ZGXJTSGNIOSYLO-UHFFFAOYSA-N 88755TAZ87 Chemical compound NCC(=O)CCC(O)=O ZGXJTSGNIOSYLO-UHFFFAOYSA-N 0.000 claims description 19
- -1 carboxyl levulan Chemical compound 0.000 claims description 18
- 239000002893 slag Substances 0.000 claims description 10
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 7
- 239000013535 sea water Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 230000021523 carboxylation Effects 0.000 claims description 2
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000001483 monosaccharide substituent group Chemical group 0.000 claims 3
- 159000000009 barium salts Chemical class 0.000 claims 1
- 159000000007 calcium salts Chemical class 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052791 calcium Inorganic materials 0.000 abstract description 8
- 239000011575 calcium Substances 0.000 abstract description 8
- 229910052788 barium Inorganic materials 0.000 abstract description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920002670 Fructan Polymers 0.000 abstract 2
- ZFTFOHBYVDOAMH-XNOIKFDKSA-N (2r,3s,4s,5r)-5-[[(2r,3s,4s,5r)-5-[[(2r,3s,4s,5r)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]oxymethyl]-3,4-dihydroxy-2-(hydroxymethyl)oxolan-2-yl]oxymethyl]-2-(hydroxymethyl)oxolane-2,3,4-triol Chemical class O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(OC[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 ZFTFOHBYVDOAMH-XNOIKFDKSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 1
- 150000002772 monosaccharides Chemical group 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000008186 active pharmaceutical agent Substances 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000011132 calcium sulphate Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008398 formation water Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ATACSYDDCNWCLV-UHFFFAOYSA-N 2-chloroacetic acid;sodium Chemical compound [Na].OC(=O)CCl ATACSYDDCNWCLV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- AIHDCSAXVMAMJH-GFBKWZILSA-N levan Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(CO[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 AIHDCSAXVMAMJH-GFBKWZILSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- AYRVGWHSXIMRAB-UHFFFAOYSA-M sodium acetate trihydrate Chemical class O.O.O.[Na+].CC([O-])=O AYRVGWHSXIMRAB-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Fats And Perfumes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubrication Of Internal Combustion Engines (AREA)
- Extraction Or Liquid Replacement (AREA)
- Compressor (AREA)
- Magnetic Resonance Imaging Apparatus (AREA)
- Detergent Compositions (AREA)
- Discharging, Photosensitive Material Shape In Electrophotography (AREA)
- Lubricants (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Control And Other Processes For Unpacking Of Materials (AREA)
- Fuel-Injection Apparatus (AREA)
- Removal Of Floating Material (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Cyclones (AREA)
Abstract
含有羧基的果聚糖如羧甲基旋复花粉在石油抽提中能成功地用于防止比如由硫酸和碳酸的钙盐。钡盐和锶盐组成的渣垢的沉积,其中在工艺用水,工艺设备或含油地层中引入了0.5—200ppm的每个单糖单元含0.3—3个羧基的含羧基果聚糖。
Description
本发明涉及一种在抽提石油中防止金属盐沉积的方法。
水广泛应用于石油抽提中。将水在压力下注入储油层。岩石中的油被水驱替进入近距离的生产井。含有油的岩石也含有水，这种水指的是地层水。这种地层水通常含有潜在的能形成渣垢的金属离子，如钡、钙和锶。在一定条件下，这些阳离子产生不溶产物。很多油田坐落在近海处，在那里可利用海水驱替石油。海水含有高浓度的硫酸盐和碳酸盐离子。当海水与地层水混合时，生成不溶盐，如硫酸钡、硫酸钙和碳酸钙。这不仅在多孔岩石中产生沉淀，而且在用于抽提石油的管道和其它设备里也产生沉积物。地层水还含有放射性原料，掺杂在生成的沉淀物中。因此，当除去沉淀时，必须采取措施以保护雇佣工人和环境。
渣垢的形成可用不同的方法来控制：
(a)对于碳酸钙结垢，加入酸或二氧化碳平衡可能移向(可溶的)碳酸氢盐。然而，加入酸得不到所希望的效果，部分原因是发生了腐蚀和海水的缓冲作用。因为需要大量的酸才能有效地降低PH值，其结果是该方法在经济上缺乏吸引力。
(b)设备可定期进行化学或机械清洗以除掉渣垢。化学清洗可用强酸或配合剂如EDTA来进行。其弊端是这种方法不能清洗处理岩石本身中的沉积物，而且这种方法会对环境带来不利因素。
(c)沉积物的形成可通过使用防垢剂得到防止。防垢剂是通过部分抑制晶体生长大大地减少渣垢形成的物质。从技术和经济的角度看，这样的防垢剂最具吸引力。
已建议或已使用的用作防垢剂的物质包括聚丙烯酸酯、聚丙烯酰胺、氨基磷酸盐和磷酸盐。比如不同的N-磷酰甲基-聚酰亚胺用作防垢剂在GB-A 2248830和WO 97/21905中描述过。这些产品的弊端在于它们是石化产品，因此是不可再生的原料，不能生物降解且对水环境有毒。用于石油抽提的化学添加剂的环境状况越来越重要，这专门用于北海的石油提取中。产品主要依据生物降解性和水生生物毒性分类，且更优选最优级产品。因此对具有良好环境状况的防垢剂的需求越来越大。而且许多公知的防垢剂，尤其是磷酸盐，在铁离子存在时性能降低；由于管线和设备的腐蚀可能产生高浓度铁离子，而导致铁渣垢如Fe(OH)3和FeCO3。
在US-A 4561982中，氧化多糖如淀粉、纤维素和羧甲基纤维素被建议作为防垢剂。在这些多糖中至少一些葡萄糖环氧化成具有下列分子式的基团：-CH(COOH)-CHA-O-CH(COOH)-O-，其中A是CH2OH,CH2OCH2COOH或COOH。建议用于冷水体系、清淤装置、地热装置等中；没提到石油提和海水。
现在已发现在石油和天然气抽提中对渣垢抑制用改进剂的需要可通过使用含羧基的旋复花粉和其它含羧基的果聚糖得到满足。这些衍生物具有优良的防垢作用，可生物降解且无毒；另外，它们的性能不受铁离子的存在影响。
在本发明中，果聚糖理解为是包括一切含有大量无水果糖单元的低聚糖和多聚糖。果聚糖具有多分散的链长度分布，可以是直链或支化链。果聚糖主要含有β-2,6键，如在左聚糖中。优选地，果聚糖主要含有β-2,1键，如在旋复花粉中。
在本发明中，含羧基的果聚糖理解为是旋复花粉或其它每个无水果糖单元含有0.3-3个羧基的果聚糖的衍生物。具体地说，该衍生物每个无水果糖单元至少含有0.8个羧基。羧基可以是羧烷基如羧甲基、羧乙基、二羧甲基或羧乙氧基羰基。这些基团可以公知的方式通过果聚糖醚化获得。羧基也可以是氧化羟亚甲基或羟甲基。也可用混合的羧基果聚糖。优选地，羧甲基的数量比其它羧基数量要大。最优选羧甲基旋复花粉(CMI)。
取代度(DS)为0.15-2.5的羧甲基旋复花粉(CMI)在WO 95/15984中和Verraest等人在JAOCS,73(1996)pp.55-62发表的一篇文章中报道过。它是通过高温下旋复花粉浓溶液与氯代醋酸钠反应制备。羧乙基旋复花粉(CEI)在WO 96/34017中有报道。旋复花粉氧化在例如WO 91/17189和WO 95/12619(C3-C4氧化，生成二羧基旋复花粉，DCI)和WO 95/07303(C6氧化)中有过报道。在混合羧基衍生物中旋复花粉首先羧甲基化，然后氧化或(优选地)其它相似的反应。
含羧基的果聚糖平均链长(=聚合度，DP)至少是3到1000。优选地，平均链长是6到60个单元。果聚糖可进行还原处理以除去还原性基团。
根据本发明能转变成羧烷基果聚糖的改性果聚糖衍生物是例如酶催化扩链的果聚糖和果聚糖水解产物，那就是说具有缩短链的果聚糖衍生物和具有改性链长的分馏产物。果聚糖如旋复花粉的分馏可通过如低温结晶(见WO 94/01849)、柱色谱法(见WO 94/12541)、膜过滤(见EP-A 440074和EP-A 627490)或乙醇的选择性沉淀的实现。先前生成的短链果聚糖的水解通过如酶催化(内-旋复花粉酶)、化学(水和酸)或多相催化(酸柱)进行实施。在羧烷基化和，如果可以的话氧化之后羟烷基化和/或交联果聚糖也可用于本发明的方法中。
羧甲基果聚糖可以以纯净物的形式使用，但也可使用直接从羧甲基化得到的技术级产品。具体地讲，已发现任何杂质，如乙二醇酸和二甘醇酸对CMI的作用没有负面影响。既可使用游离酸又可使用盐，如钠盐、钾盐或铵盐。
含羧基果聚糖，特别是CMI在工艺用水中的浓度通常在0.5-200ppm(重量份数)之间，特别是在2-50ppm之间。也可使用含羧基果聚糖和其它防垢剂如聚丙烯酸酯或磷酸盐的混合物，比例优选为至少1份含羧基的果聚糖对1份其它试剂。
防垢剂可加入海水并以这种方式用泵入含油地层中。也可在产生大量沉淀工艺设备的特定位置引入防垢剂。防垢剂也可连续注入油井底部的液体中。然而，更进一步技术就是“压榨”技术，在此技术中将防垢剂引入岩石中。防垢剂沉淀和/或地层将其吸收。随着时间的推移通过解吸释放出足够多的防垢剂以防止结垢形成。数月后，结垢配制剂储备用完，再重复此过程。此应用不局限于海上石油提取，也可用于在海上和陆地上以水作为驱替剂的提取过程。
实施例1
确定CMI(DP约等于10)对碳酸钙的防垢作用。将氯化钙溶液和碳酸钠溶液混合制得一种饱和碳酸钙溶液，所形成的碳酸钙的最大量为95毫克/升。将1毫克/升或5毫克/升的防垢剂加入该溶液。溶液PH值调节到10.0，然后在75℃静置，震荡。20小时后用White Band漏斗过滤，确定滤液的钙含量。防垢剂的作用以不加防垢剂(0％防垢剂)实验的钙值和没有沉淀产生(100％防垢剂)的钙值为基准计算。此实验得到如表1所示的结果。
表1
实施例2
| 浓度为1mg/l的防垢作用 | 浓度为5mg/l的防垢作用 | |
| CMI DS=1.0 | 88 | 100 |
| CMI DS=2.0 | 21 | 100 |
| 聚丙烯酸酯4500 | 60 | 100 |
确定CMI(DP约等于10)对硫酸钙的防垢作用。将氯化钙溶液和硫酸钠溶液混合制得一种饱和硫酸钙溶液，且所形成的硫酸钙溶液思的最大量为95毫克/升。将1毫克/升、5毫克/升或10毫克/升的防垢剂加入该溶液。溶液PH值调节到7.0，然后在30℃静置。20小时后用Red Band漏斗过滤，确定滤液的钙含量。防垢剂的作用以不加防垢剂(0％防垢剂)实验的钙值和没有沉淀产生(100％防垢剂)的钙值为基准计算。此实验得到如表2所示的结果。
表2
实施例3
| 浓度为1mg/l的防垢作用 | 浓度为5mg/l的防垢作用 | 浓度为10mg/l的防垢作用 | |
| CMI DS=1.0 | 11.7 | 77.8 | 90.5 |
| CMI DS=2.0 | 23.1 | 90.0 | 93.0 |
| 磷酸盐 | 35.9 | 87.6 | 89.2 |
| 聚丙烯酸酯4500 | 29.1 | 89.7 | 92.4 |
重复实施例2(硫酸钙渣垢抑制)，只是溶液是7天后而不是20小时后过滤。结果如表3所示。
表3
实施例4
| 浓度为1mg/l时的防垢作用(％) | 浓度为5mg/l时的防垢作用(％) | 浓度为10mg/l时的防垢作用(％) | |
| CMI DS=1.0 | 5.2 | 81.0 | 87.3 |
| CMI DS=2.0 | 8.0 | 92.4 | 93.9 |
| 磷酸盐 | 2.7 | 56.9 | 86.9 |
| 聚丙烯酸酯4500 | 5.3 | 88.6 | 89.6 |
确定CMI(DP约等于10)对硫酸钡的防垢作用。将氯化钙溶液(380mg/l)和硫酸钠溶液(3350mg/l)以1∶1比例混合制得一种饱和硫酸钡溶液，所形成的硫酸钡溶液的最大量是210毫克/升。将5毫克/升、10毫克/升或15毫克/升的防垢剂加入该溶液。溶液PH值通过加入每100毫升含1毫升醋酸盐的缓冲液(每100毫升含13.6克醋酸钠三水合物和0.5克醋酸)调节到5.5，然后在80℃静置。10小时后真空过滤使其通过0.45um的Milipore过滤器，确定滤液的钡含量。防垢剂的作用以不加防垢剂(0％防垢剂)实验的钡值和没有沉淀产生(100％防垢剂)的钡值为基准计算。结果列于表4中。
表4
实施例5
| 浓度为5mg/l的防垢作用 | 浓度为10mg/l的防垢作用 | 浓度为15mg/l的防垢作用 | |
| CMI DS=1.0,DP=10 | 15.0 | 27.5 | 57.5 |
| CMI DS=2.0.DP=10 | 78.0 | 96.5 | 100 |
| CMI DS=2.0,DP=20 | 82.5 | 98.0 | 100 |
| 五聚磷酸盐(DETPMP) | 18.0 | 38.5 | 55.5 |
重复实施例4，除了硫酸钡溶液含有38毫克/升的Fe2+。结果列于表5中。
表5
| 浓度为5mg/l的防垢作用 | 浓度为10mg/l的防垢作用 | 浓度为15mg/l的防垢作用 | |
| CMI DS=2.0,DP=10 | 75.0 | 92.0 | 98.5 |
| CMI DS=2.0.DP=20 | 80.5 | 96.0 | 99.0 |
| 五聚磷酸盐(DETPMP) | 12.0 | 21.5 | 34.5 |
Claims (11)
1．一种在石油提取中使用一种聚羧基化合物防止渣垢沉积的方法，其特征在于在工艺用水、工艺设备或含油地层中引入了每个单糖单元含0.3-3个羧基的含羧基果聚糖。
2．如权利要求1所述的方法，其中将含羧基果聚糖加入工艺用水中，浓度为0.5-200ppm，优选为2-50ppm；
3．如权利要求1或2所述的方法，其中含羧基果聚糖每单糖单元至少含有0.8个羧基；
4．如权利要求1-3之一所述的方法，其中含羧基果聚糖每单糖单元至少含有0.7-2.5个羧甲基；
5．如权利要求1-4之一所述的方法，其中含羧基果聚糖是平均聚合度为6-60的一种羧甲基旋复花粉；
6．如权利要求1-5之一所述的方法，其中渣垢包括钙盐、钡盐和/或锶盐；
7．如权利要求1-6之一所述的方法，其中渣垢包括碳酸盐和/或硫酸盐；
8．如权利要求1-7之一所述的方法，其中渣垢包括铁盐；
9．如权利要求1-8之一所述的方法，其中使用了一种直接从果聚糖羧烷基化得到的产物；
10．如权利要求1-8之一所述的方法，其中使用了一种纯净的羧烷基果聚糖；
11．如权利要求1-10之一所述的方法，其中工艺用水是海水。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1009356 | 1998-06-09 | ||
| NL1009356A NL1009356C2 (nl) | 1998-06-09 | 1998-06-09 | Werkwijze voor het voorkomen van afzetting bij de winning van olie. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1305563A true CN1305563A (zh) | 2001-07-25 |
| CN1119500C CN1119500C (zh) | 2003-08-27 |
Family
ID=19767280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99807192A Expired - Fee Related CN1119500C (zh) | 1998-06-09 | 1999-06-09 | 在石油开采中防止结垢沉积的方法 |
Country Status (23)
| Country | Link |
|---|---|
| US (1) | US6613899B1 (zh) |
| EP (1) | EP1093541B2 (zh) |
| JP (1) | JP2002517651A (zh) |
| CN (1) | CN1119500C (zh) |
| AT (1) | ATE241080T1 (zh) |
| AU (1) | AU748920B2 (zh) |
| BG (1) | BG105034A (zh) |
| BR (1) | BR9910996A (zh) |
| CA (1) | CA2334782C (zh) |
| DE (1) | DE69908128T2 (zh) |
| DK (1) | DK1093541T3 (zh) |
| ES (1) | ES2197691T3 (zh) |
| HU (1) | HUP0102433A3 (zh) |
| ID (1) | ID26821A (zh) |
| IL (1) | IL140086A0 (zh) |
| MX (1) | MXPA00012232A (zh) |
| NL (1) | NL1009356C2 (zh) |
| NO (1) | NO318085B1 (zh) |
| NZ (1) | NZ508679A (zh) |
| PT (1) | PT1093541E (zh) |
| RU (1) | RU2234596C2 (zh) |
| TR (1) | TR200003659T2 (zh) |
| WO (1) | WO1999064716A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298416C (zh) * | 2001-10-09 | 2007-02-07 | 蒂西苏克拉菲纳德里有限公司 | 疏水性改性糖类表面活性剂 |
| CN102428040A (zh) * | 2009-03-17 | 2012-04-25 | 德凯斯特公司 | 用于抑制钙盐结垢的组合物 |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1009379C2 (nl) † | 1998-06-11 | 1999-12-15 | Cooperatie Cosun U A | Dispergeermiddel. |
| NL1014985C2 (nl) * | 2000-04-19 | 2001-10-24 | Co Peratie Cosun U A | Sequestreren. |
| FR2897362B1 (fr) * | 2006-02-13 | 2008-04-18 | Inst Francais Du Petrole | Methode de traitement des puits par emulsions de petite taille contenant des additifs |
| DK2148908T3 (en) * | 2007-05-08 | 2018-03-26 | Solvay Usa Inc | POLYSACCHARID-BASED STONE INHIBITORS |
| US7977283B2 (en) * | 2008-06-27 | 2011-07-12 | Baker Hughes Incorporated | Method of minimizing or reducing salt deposits by use of a fluid containing a fructan and derivatives thereof |
| WO2010041025A1 (en) * | 2008-10-10 | 2010-04-15 | Halliburton Energy Services, Inc. | Ceramic coated particulates |
| US20100089578A1 (en) * | 2008-10-10 | 2010-04-15 | Nguyen Philip D | Prevention of Water Intrusion Into Particulates |
| US8881811B2 (en) | 2008-10-10 | 2014-11-11 | Halliburton Energy Services, Inc. | Additives to suppress silica scale build-up and methods of use thereof |
| US9976070B2 (en) | 2010-07-19 | 2018-05-22 | Baker Hughes, A Ge Company, Llc | Method of using shaped compressed pellets in well treatment operations |
| US10822536B2 (en) | 2010-07-19 | 2020-11-03 | Baker Hughes, A Ge Company, Llc | Method of using a screen containing a composite for release of well treatment agent into a well |
| US9010430B2 (en) | 2010-07-19 | 2015-04-21 | Baker Hughes Incorporated | Method of using shaped compressed pellets in treating a well |
| US9012376B2 (en) * | 2011-03-14 | 2015-04-21 | Halliburton Energy Services, Inc. | Inulin as corrosion inhibitor |
| US8664168B2 (en) | 2011-03-30 | 2014-03-04 | Baker Hughes Incorporated | Method of using composites in the treatment of wells |
| US20130269937A1 (en) * | 2012-04-12 | 2013-10-17 | Halliburton Energy Services, Inc. | Acidizing Fluids Comprising a Salt Block Inhibitor and Methods for Use Thereof |
| US9950937B1 (en) * | 2012-09-25 | 2018-04-24 | Stephen R. Temple | Methods for treating liquid streams containing quaternary ammonium compounds |
| US9963366B2 (en) * | 2013-03-15 | 2018-05-08 | Stephen R. Temple | Methods for treating liquid streams containing quaternary ammonium compounds |
| WO2016014310A1 (en) | 2014-07-23 | 2016-01-28 | Baker Hughes Incorporated | Composite comprising well treatment agent and/or a tracer adhered onto a calcined substrate of a metal oxide coated core and a method of using the same |
| US10641083B2 (en) | 2016-06-02 | 2020-05-05 | Baker Hughes, A Ge Company, Llc | Method of monitoring fluid flow from a reservoir using well treatment agents |
| US10413966B2 (en) | 2016-06-20 | 2019-09-17 | Baker Hughes, A Ge Company, Llc | Nanoparticles having magnetic core encapsulated by carbon shell and composites of the same |
| AU2017400534B2 (en) * | 2017-02-27 | 2023-05-11 | Bl Technologies, Inc. | Sulfate scale inhibition in high pressure and high temperature applications |
| US12060523B2 (en) | 2017-07-13 | 2024-08-13 | Baker Hughes Holdings Llc | Method of introducing oil-soluble well treatment agent into a well or subterranean formation |
| WO2019013799A1 (en) | 2017-07-13 | 2019-01-17 | Baker Hughes, A Ge Company, Llc | SYSTEM FOR DELIVERING OLEO-SOLUBLE WELL PROCESSING AGENTS AND METHODS OF USE THEREOF |
| EP3704206A1 (en) | 2017-11-03 | 2020-09-09 | Baker Hughes Holdings Llc | Treatment methods using aqueous fluids containing oil-soluble treatment agents |
| US10961444B1 (en) | 2019-11-01 | 2021-03-30 | Baker Hughes Oilfield Operations Llc | Method of using coated composites containing delayed release agent in a well treatment operation |
| US11655413B2 (en) | 2021-02-04 | 2023-05-23 | Saudi Arabian Oil Company | Methods for removing sulfate ions from seawater to form injection fluids |
| US11746280B2 (en) * | 2021-06-14 | 2023-09-05 | Saudi Arabian Oil Company | Production of barium sulfate and fracturing fluid via mixing of produced water and seawater |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2557473A (en) † | 1947-10-14 | 1951-06-19 | Phillips Petroleum Co | Drilling fluids and methods of using same |
| US3411580A (en) * | 1966-09-28 | 1968-11-19 | Byron Jackson Inc | Mud removal method |
| US3596766A (en) * | 1969-03-28 | 1971-08-03 | Nat Lead Co | Scale inhibition |
| JPS5976598A (ja) * | 1982-10-25 | 1984-05-01 | Mitsubishi Gas Chem Co Inc | スケ−ル防止剤 |
| FR2570755B1 (fr) * | 1984-09-25 | 1986-11-21 | Schlumberger Cie Dowell | Nouvelles applications du scleroglucane dans le domaine du traitement des puits d'hydrocarbures comme agent de mise en suspension de particules solides ou de bulles |
| FR2570753B1 (fr) * | 1984-09-25 | 1986-12-12 | Schlumberger Cie Dowell | Nouvelles applications du scleroglucane comme fluide de nettoyage des conduites d'installations petrolieres |
| GB2248830A (en) * | 1990-10-04 | 1992-04-22 | Britoil Plc | Method for inhibiting scale formation |
| NL9302163A (nl) † | 1993-12-10 | 1995-07-03 | Univ Delft Tech | Gecarboxymethyleerde oligo- en polysacchariden als kristallisatie inhibitors. |
| NL1003776C2 (nl) * | 1996-08-09 | 1998-02-20 | Cooperatie Cosun U A | Milieuvriendelijke complexanten voor zware metalen |
| NL1004738C2 (nl) * | 1996-12-10 | 1998-06-11 | Cooperatie Cosun U A | Fructaan-polycarbonzuur. |
-
1998
- 1998-06-09 NL NL1009356A patent/NL1009356C2/nl not_active IP Right Cessation
-
1999
- 1999-06-09 AT AT99955517T patent/ATE241080T1/de not_active IP Right Cessation
- 1999-06-09 HU HU0102433A patent/HUP0102433A3/hu unknown
- 1999-06-09 JP JP2000553697A patent/JP2002517651A/ja active Pending
- 1999-06-09 BR BR9910996-4A patent/BR9910996A/pt active Search and Examination
- 1999-06-09 IL IL14008699A patent/IL140086A0/xx unknown
- 1999-06-09 DK DK99955517T patent/DK1093541T3/da active
- 1999-06-09 WO PCT/NL1999/000358 patent/WO1999064716A1/en not_active Application Discontinuation
- 1999-06-09 MX MXPA00012232A patent/MXPA00012232A/es active IP Right Grant
- 1999-06-09 ID IDW20002539A patent/ID26821A/id unknown
- 1999-06-09 CA CA002334782A patent/CA2334782C/en not_active Expired - Lifetime
- 1999-06-09 AU AU42938/99A patent/AU748920B2/en not_active Expired
- 1999-06-09 PT PT99955517T patent/PT1093541E/pt unknown
- 1999-06-09 ES ES99955517T patent/ES2197691T3/es not_active Expired - Lifetime
- 1999-06-09 RU RU2001101453/03A patent/RU2234596C2/ru active
- 1999-06-09 TR TR2000/03659T patent/TR200003659T2/xx unknown
- 1999-06-09 DE DE69908128T patent/DE69908128T2/de not_active Expired - Fee Related
- 1999-06-09 US US09/719,239 patent/US6613899B1/en not_active Expired - Lifetime
- 1999-06-09 CN CN99807192A patent/CN1119500C/zh not_active Expired - Fee Related
- 1999-06-09 EP EP99955517A patent/EP1093541B2/en not_active Expired - Lifetime
- 1999-06-09 NZ NZ508679A patent/NZ508679A/xx unknown
-
2000
- 2000-12-05 NO NO20006173A patent/NO318085B1/no not_active IP Right Cessation
- 2000-12-08 BG BG105034A patent/BG105034A/xx unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298416C (zh) * | 2001-10-09 | 2007-02-07 | 蒂西苏克拉菲纳德里有限公司 | 疏水性改性糖类表面活性剂 |
| CN102428040A (zh) * | 2009-03-17 | 2012-04-25 | 德凯斯特公司 | 用于抑制钙盐结垢的组合物 |
| CN102428040B (zh) * | 2009-03-17 | 2016-03-02 | 伊塔尔麦奇化学股份公司 | 用于抑制钙盐结垢的组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ508679A (en) | 2003-02-28 |
| BR9910996A (pt) | 2001-02-13 |
| WO1999064716A1 (en) | 1999-12-16 |
| NO20006173D0 (no) | 2000-12-05 |
| EP1093541A1 (en) | 2001-04-25 |
| EP1093541B1 (en) | 2003-05-21 |
| CN1119500C (zh) | 2003-08-27 |
| JP2002517651A (ja) | 2002-06-18 |
| BG105034A (en) | 2001-09-28 |
| CA2334782A1 (en) | 1999-12-16 |
| ID26821A (id) | 2001-02-15 |
| CA2334782C (en) | 2007-12-18 |
| DE69908128T2 (de) | 2003-12-18 |
| HUP0102433A3 (en) | 2003-01-28 |
| TR200003659T2 (tr) | 2001-06-21 |
| HUP0102433A2 (hu) | 2001-10-28 |
| EP1093541B2 (en) | 2010-08-25 |
| NL1009356C2 (nl) | 1999-12-10 |
| AU748920B2 (en) | 2002-06-13 |
| ATE241080T1 (de) | 2003-06-15 |
| DE69908128D1 (de) | 2003-06-26 |
| NO318085B1 (no) | 2005-01-31 |
| MXPA00012232A (es) | 2003-04-25 |
| RU2234596C2 (ru) | 2004-08-20 |
| ES2197691T3 (es) | 2004-01-01 |
| IL140086A0 (en) | 2002-02-10 |
| US6613899B1 (en) | 2003-09-02 |
| NO20006173L (no) | 2001-02-07 |
| DK1093541T3 (da) | 2003-06-23 |
| AU4293899A (en) | 1999-12-30 |
| PT1093541E (pt) | 2003-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1119500C (zh) | 在石油开采中防止结垢沉积的方法 | |
| BRPI0811549B1 (pt) | Método de inibição de carepa em sistemas aquosos | |
| WO1994006730A1 (en) | Water and soil treatment method | |
| EP1060135B1 (en) | Process for controlling scale in the sugar process | |
| EP1464627B1 (de) | Verfahren zur Verhinderung von Ablagerungen in Wasser | |
| US7645722B2 (en) | Aloe derived scale inhibitor | |
| WO1998025972A1 (en) | Fructan-polycarboxylic acid | |
| CN113769588A (zh) | 一种工业废水处理用ro反渗透膜阻垢剂及其使用方法 | |
| CN114426523B (zh) | 一种无磷缓蚀阻垢剂及其制备方法与应用 | |
| WO1988006143A1 (en) | Anti-scaling compounds | |
| CZ20004516A3 (cs) | Způsob prevence tvorby usazenin při těžbě ropy | |
| CN109970219A (zh) | 反渗透阻垢剂及其制备方法和应用 | |
| CN1063825C (zh) | 油田注入水处理方法 | |
| US20080132431A1 (en) | Scale squeeze treatment methods and systems | |
| US20100075870A1 (en) | Process using aloe for inhibiting scale | |
| CN112591901A (zh) | 一种矿井水深度处理药剂及其使用方法 | |
| JP3122602B2 (ja) | リン及びアンモニア含有排水の処理方法 | |
| MXPA00008093A (en) | Process for controlling scale in the sugar process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |