TW546370B - Method of removing asphaltenes or petroleum waxes deposited in, or preventing, or inhibiting, the deposition of asphaltenes or petroleum waxes in, oil treatment equipment - Google Patents
Method of removing asphaltenes or petroleum waxes deposited in, or preventing, or inhibiting, the deposition of asphaltenes or petroleum waxes in, oil treatment equipment Download PDFInfo
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- TW546370B TW546370B TW90106069A TW90106069A TW546370B TW 546370 B TW546370 B TW 546370B TW 90106069 A TW90106069 A TW 90106069A TW 90106069 A TW90106069 A TW 90106069A TW 546370 B TW546370 B TW 546370B
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- 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
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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Description
546370 五、發明說明(1) 本發明係 有關由此等 原油為多 低分子量組 低分子量產 苯主要係由 子量的物質 油來源改變 族化合物, 質取代基鏈 呈細粒或小 油脂的樹脂 助。石油壤 脂族4匕合物 質。通常其 於原油。 精煉時, ,然後形成 的較短鏈院 部分而結束 於製造及 溫度下,瀝 其接觸表面 井或其它油 有關於 設備去 種成分 分,大 物女口 it匕等組 ,包括 ,但典 包括雜 。歷青 片存在 狀物質 為長鏈 。其常 可溶於 油生產 除瀝青 之混合 半為烴 石腦油 分獲得 稱作遞 型為多 環族特 烯可能 。其於 以及大 ,典型 被描述 原油, 此等物質通常 產物中有用部 或缔,或以靜 〇 加工過程中, 青缔及石油蠖 上的沉積物。 管,或可於產 及精煉設備去除沉積物,特別-係 稀及/或石油堪之沉積物。 物其隨來源改變Q典型包括相對 類包括脂族及芳族化合物。相對 、汽油、柴油或輕燃油、苯及甲 。通常原油也包括具有遠較高分 青烯及石油堪的物質。瀝青稀隨 環化合物,通常為芳族或部分芳 別N及S原子,以及典型帶有多脂 非真正可溶於大部分原油,但^可 油之分散液係經由存在有俗稱石 部分產油岩層的溫度相當高之 為(:15至(:1(](},且通常主要為開鏈 為鏈烷烴且可為直鏈或分支鏈物 特別於大半產油岩層溫度時可溶 係裂解成為較低分小量化合物 分例如石油蠟,其可被轉成有用 止底德分例如作為瀝青產物之一 以及特別於低於產油形成溫度之 可由大量油分離,變成固化成為 此等沉積物可能封阻油通過的油 油期間以及煉油操作早期階段沉546370 V. Description of the invention (1) The present invention relates to resins in which such crude oil is a low-molecular weight group and low-molecular-weight benzene is produced mainly by sub-quantitative substances and oil sources, and the resin is a family of fine-grained or small-granular substituent chains. help. Petroleum soil aliphatic 4 dagger composition. Usually it is for crude oil. During the refining, the shorter chain part then formed at the end of the manufacturing and temperature, the contact surface of the well or other oil is related to the equipment to deseed the components, the large female mouth, it and other groups, including, but the code includes miscellaneous . Liqing tablets have long chains. It is often soluble in oil production, except for the removal of bitumen, semi-hydrocarbon naphtha, and it is possible to obtain a polycyclic terpene which is called as a transgene. It is described as well as large, typically crude oil, and these materials are often used in products, or in the process of static, sedimentation on the association and petroleum. Pipe, or may be used in production and refining equipment to remove sediments, especially-thin and / or petroleum deposits. It varies depending on the source. Q typically includes relative classes including aliphatic and aromatic compounds. Relative, gasoline, diesel or light fuel oil, benzene and methylbenzene. Usually crude oil also includes substances with much higher cyanine and petroleum content. Asphalt rare ring compounds, usually aromatic or partially aromatic N and S atoms, and typically with a lot of fats are not truly soluble in most crude oils, but oily dispersions are produced through the existence of what is commonly known as stone partial oil production The temperature of the rock formation is quite high (: 15 to (: 1 () (}), and it is usually mainly open-chain paraffins and can be straight or branched. In particular, the soluble system cracks at the temperature of most semi-productive rock formations. Lower fractions of small amounts of compounds such as petroleum waxes, which can be converted into useful bases such as as one of the bitumen products and can be separated by large amounts of oil, especially below the temperature at which oil is produced, becoming solidified into such deposits. Sinking during the oil blocking process and early stages of refining operations
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五、發明說明(2) 積於分離槽或儲存槽底部。要緊需去除此等沉積物 管的阻塞以及油槽容量的縮小。 、以防抽 及油 但環 用的 習知芳族溶劑如二甲苯偶而組合分散劑用於甴油总 槽去除瀝青烯及石油蠟。此等芳族材料為良好溶叫& 境考慮造成須降低此等揮發性芳族化合物用於產業废 比例的壓力。 u 本發明係基於發現芳族羧酸,特別苯甲酸之某此々 _ 基酯類為沉積於油及精煉設備之極為有效溶劑,^ ^別燒 青烯與石油蠟之有效溶劑,且比較目前用於此等^途為# 甲苯稀溶劑於環保上遠更不排斥。 *之一 如此本發明提供一種於油井、油管或油槽去除或防止一。、 抑制歷青烯及/或石油蠟沉積之方法,該方法包含讓㉖主< 烯及/或石油蝶或毗鄰瀝青烯及/或石油壤預期沉積月 油井、油管或油槽接觸一種包括至少一種式(I)化人物 溶劑: R!-(A0 )n-〇〇C-(CH2 )fn-Ph-(R2 )p ⑴ 其中 _ R1為Ci至(^烴基,特別c3至c18烷基或烯基; A0為伸烷基氧基’特別伸乙基氧基或伸丙基氧基,且可A (聚)伸烷基氧基鏈改變; /° η為0或1至1〇〇 ,較佳為〇 ; m為〇、1或2,較佳為〇 ;以及5. Description of the invention (2) It is accumulated in the bottom of the separation tank or storage tank. There is an urgent need to remove the blockage of these sediment pipes and the reduction of oil tank capacity. In order to prevent pumping and oil, the conventional aromatic solvents such as xylene are occasionally combined with dispersing agents to remove asphaltene and petroleum wax from the total oil tank. These aromatic materials are well-solved & environmental considerations have created pressure to reduce the proportion of these volatile aromatic compounds used in industrial waste. u The present invention is based on the discovery of aromatic carboxylic acids, especially benzoic acid, which is a very effective solvent for depositing in oil and refining equipment. Used for these ^ ## toluene dilute solvent is far more exclusive in environmental protection. * One Thus, the present invention provides a method for removing or preventing oil wells, tubing or oil tanks. A method for inhibiting the deposition of azulene and / or petroleum wax, the method comprising contacting the main host < ene and / or petroleum butterfly or adjacent asphaltene and / or petroleum soil with the expected deposition of oil wells, tubing or oil tanks, including at least one Solvents of formula (I): R!-(A0) n-〇〇C- (CH2) fn-Ph- (R2) p ⑴ where _R1 is Ci to (^ hydrocarbon group, especially c3 to c18 alkyl or olefin A0 is an alkyleneoxy group, in particular an ethyloxy group or a propyloxy group, and can be changed by the A (poly) alkyleneoxy chain; / ° η is 0 or 1 to 100, compared with Preferably 0; m is 0, 1 or 2, preferably 0; and
ΪΪΐΐ:其可以料基取代;其中各俯分別為CJC 说基或Μ基;以及ρ為〇、丨或2,較佳制; GΪΪΐΐ: it can be substituted by a material group; wherein each is CJC group or M group; and ρ is 0, 丨 or 2, preferably made; G
第6頁 ^46370 五、發明說明⑶ 以及隨後由油井、油營 ^ 分散的遞青稀及/或2 /曹去除帶有軟化的、溶解 用於本發明之式⑴ΐ = =二優點為比烯基較為穩定u為院基或歸基。使 成;ί::Γ”括單一雙鍵,二;維持流體 至[。鏈如c3至(:6烷基。 為相對短鏈,如c 基)’第二丁基(丁_2、2,\為分支例如為異丙基(丙1 三丁基及/或2-乙美己ΐ 異丁基(2~甲基—丙一 1 —基),第 此方面而言二己級基:卑降低醋水解的…度。就 鏈燒基醋類包括乙基、+其、、丙基。其它可使用的相對短 如丙基、丁基、戊A t及其它直鏈烷基苯甲酸酯例 為具有低黏度酸醋。相對短鏈醋效果 於溶劑之低蠟時,需要較長鏈醋俾改良壤 或烯如此,R^c^2◦特別C8至ci4基 _,二Si4 例如混合_ (如混合k/C13烧基)苯甲酸 ί支例如I乙基己基或異—壬基或分支鏈Q燒 t 1 〇 ^明之異硬脂基(實際為主要為分支CH至匕2烷基混 "丄可有平均鍵長度接近〇18)。未飽和長鏈基包括油 二二右,用較長鏈長度基,特別比。更長之基時,較佳為 :I括1支及/或未飽和,及/或使用此等酯之混合物,其 足成液L i曰’而直鏈飽和酯化合物為固體因而更難以使 用〇 _Page 6 ^ 46370 V. Description of the invention ⑶ and subsequent dilute thinning and / or 2 / Cao removed by oil wells and oil camps ^ remove the formula with softening and dissolving for use in the invention ⑴ΐ = = two advantages are than ene The base is more stable, u is the base or the base. To make; ί :: Γ "encompass a single double bond, two; maintain fluid to [. Chain such as c3 to (: 6 alkyl. Is a relatively short chain, such as c group) 'second butyl (but_2, 2, \ is a branch such as isopropyl (propyl 1 tributyl and / or 2-ethylhexyl isopropyl (2-methyl-propane-1-yl), and in this respect, dihexyl : Reduces the degree of hydrolysis of vinegar. Alkali-based vinegars include ethyl, + ,, and propyl. Other relatively short, such as propyl, butyl, pentyl, and other straight-chain alkyl benzyl Examples of acid esters are acid vinegars with low viscosity. When relatively short-chain vinegars have the effect of low waxes in solvents, longer chain vinegars are needed to improve the soil or ene. R ^ c ^ 2. Especially C8 to ci4 groups. Mixed _ (such as mixed k / C13 alkyl) benzoic acid, such as I ethylhexyl or iso-nonyl or branched chain Q t 1 0 ^ isostearyl (actually mainly branched CH to alkane 2 The basic compound "quot may have an average bond length close to 〇18). Unsaturated long chain groups include oil two, two, right, with a longer chain length group, especially the ratio. For longer groups, it is preferred: I include 1 branch And / or unsaturated, and / or use of these esters Mixture, which is sufficient to form a liquid Li, and the linear saturated ester compound is a solid, so it is more difficult to use.
第7頁 546370 五、發明說明(4) 雖然用於酯之羧酸可為二氫桂皮酸或苯基乙酸,極為-希 望為苯曱酸,換言之較佳m為0。同理,雖然酸之笨環可經 取代,但較佳為無取代,換言之較佳P為0。本發明使用之 酯包括式(I ) ( A〇)n之(聚)伸烷基氧基鏈,介於羧基與R1基 間。(聚)伸烷基氧基鏈當存在時,較佳為(聚)伸乙基氧基 鍵、(聚)伸丙基氧基鏈或包括伸乙基氧基及伸丙基氧基殘 基之鍵。通常较佳於酯不包括此種鏈,換言之較佳η為0。 特別用於溶解瀝青烯,特別有用的酯為苯甲酸異丙酯 ,本發明特別包括一種本發明之方法其中溶劑為或包括苯 甲酸異丙酯。笨甲酸異丙酯具有多種性質組合,因此讓^其 作為溶劑格外#用。至於純質材料,具有寬廣之液體範 圍,具有高沸點(沸點約2 1 9 °C )於低於通常預期之環境溫 度之溫度下,缑持流體(傾點< -6 0 °C );具有閃火點(約9 9 °C ),故可歸類為不可燃,以及於正常使用條件下具有低 蒸汽壓;具有鎮似水之密度(於25 t為1. 0 0 8千克/升);以 及具有低黏度(於25 °C為2. 32厘史(cSt);藉U型管方法測 量相當於2.34 mPa.s)。 供比較用,其它烷基苯甲酸酯具有黏度(於25 °C )如後: 苯甲酸乙酯:1.9厘史;苯曱酸2-乙基己酯:6. 1厘史;苯 甲酸壬酯:7. 5厘史;苯甲酸(混合C12/C13烷酯):14厘史; 以及苯曱酸異硬脂酯:3 0厘史。 為了提供瀝青烯及石油蠟二者之溶解度平衡,具有多種 R1基之混合酯或式(I )化合物攙合由於具有可匹配瀝青烯 及石油蝶技合的溶劑性質的組合故較為有利。此種攙合物Page 7 546370 V. Description of the invention (4) Although the carboxylic acid used for the ester may be dihydrocinnamic acid or phenylacetic acid, it is highly desirable to be phenylarsinic acid, in other words, m is preferably 0. Similarly, although the dull ring of an acid may be substituted, it is preferably unsubstituted, in other words, P is preferably 0. The ester used in the present invention includes a (poly) alkyleneoxy chain of the formula (I) (Ao) n, which is between the carboxyl group and the R1 group. When a (poly) alkyleneoxy chain is present, it is preferably a (poly) ethyleneoxy bond, a (poly) alkyleneoxy chain, or a residue including an ethyloxy group and a methyloxy group Key. It is generally preferred that the ester does not include such chains, in other words it is preferred that n is zero. Particularly useful for dissolving asphaltenes, a particularly useful ester is isopropyl benzoate. The present invention specifically includes a method of the present invention wherein the solvent is or includes isopropyl benzoate. Isopropyl behenate has multiple combinations of properties, so it is particularly useful as a solvent. As for pure materials, it has a wide liquid range, has a high boiling point (boiling point is about 219 ° C), and holds fluid at a temperature lower than the generally expected ambient temperature (pour point < -6 0 ° C); With a flash point (about 9 9 ° C), it can be classified as non-combustible and has a low vapor pressure under normal use conditions; it has a water-like density (at 25 t of 1.0 8 kg / liter ); And has a low viscosity (2.35 cSt at 25 ° C; equivalent to 2.34 mPa.s measured by U-tube method). For comparison, other alkyl benzoates have viscosity (at 25 ° C) as follows: ethyl benzoate: 1.9% history; 2-ethylhexyl benzoate: 6.1% history; nonylbenzoate Esters: 7.5 cents of history; benzoic acid (mixed C12 / C13 alkyl esters): 14 cents of history; and isostearyl benzoate: 30 cents of history. In order to provide the solubility balance of both asphaltene and petroleum wax, a mixed ester having multiple R1 groups or a compound of formula (I) is advantageous because it has a combination of solvent properties that can match asphaltene and petroleum butterfly technology. This compound
546370 五、發明說明⑸ 之混合酯具有額外優點為,其比純質特別具有類似的總J?1 碳數之直鏈飽和化合物更為呈液態。 本發明方法使用的溶劑可全然為一或多種式(I)化合物 ,或可含有其它溶劑之混合物。雖然可含括二曱苯類,但 由於二甲笨類或其它含有相當比例芳族烴類之溶劑對環境 造成不良影響,故不可用作為任何此種混合載劑流體的主 要成分。與鏈烷烴液體溶劑之混合物可改良石油蠟類之溶 解度,但可能降低瀝青烯類之溶解度。其它溶劑如水溶性 醇類也可含括作為添加劑之載劑(參見下文)或用以改良與 使用的水性材料之相容性。此種混合溶劑中,其比例係^依 據沉積於油管或油槽之材料之特定性質決定,且可能依據 遞青稀及石油壤間之平衡及組成細節決定。當使用混合物 時,式(I)化合物典型之存在量係占使用的載劑流體總重 之至少25%,通常至少40%,更常至少50%,較佳至少60%, 及特佳至少7 5 %。當存在時,其它溶劑成分之用量濃度典 型係占使用的載劑流體總重之1至7 5,通常1至4 0 %,更佳2 至2 5 ,及特隹5至1 5 %重量比。 "13 為了輔助分散遞青烯及/或石油墙,溶劑可包括分散劑 ,特別非離子性界面活性劑及分散劑如醇烷氧酸酯類;聚 異丁烯丁二酐類(PIBSA’ s)與醇烷氧酸酯類特別C1Q至C18如 至C15醇乙氧酸酯類之反應產物;PIBSA’ s與烷醇胺類如 及三-乙醇胺之反應產物;以及聚山梨糖醇脂肪酸酯 類,特別,一酯類及特別未飽和脂肪酸之酯類例如聚山梨 糖醇一油酸旨;磺酸分散劑如烷基芳基磺酸;或含樹脂分546370 V. Description of the invention The mixed ester of ⑸ has the additional advantage that it is more liquid than pure straight chain saturated compounds with similar total J? 1 carbon number. The solvent used in the method of the invention may be entirely one or more compounds of formula (I), or it may contain a mixture of other solvents. Although it can contain dibenzobenzenes, it is unsuitable as the main component of any such mixed carrier fluids because xylenes or other solvents containing a considerable proportion of aromatic hydrocarbons have adverse effects on the environment. Mixtures with paraffinic liquid solvents can improve the solubility of petroleum waxes, but may reduce the solubility of asphaltenes. Other solvents such as water-soluble alcohols may also include carriers as additives (see below) or to improve compatibility with the water-based materials used. The proportion of this mixed solvent is determined by the specific properties of the material deposited in the oil pipe or oil tank, and may be determined by the balance and composition details of the thinning and petroleum soil. When a mixture is used, the compound of formula (I) is typically present in an amount of at least 25%, usually at least 40%, more usually at least 50%, preferably at least 60%, and particularly preferably at least 7% of the total weight of the carrier fluid used. 5%. When present, the concentration of other solvent components is typically 1 to 75, usually 1 to 40%, more preferably 2 to 25, and 5 to 15% by weight of the total weight of the carrier fluid used. . " 13 In order to assist in dispersing blueene and / or petroleum walls, the solvent may include dispersants, especially nonionic surfactants and dispersants such as alcohol alkoxylates; polyisobutylene succinic anhydrides (PIBSA's) Reaction products with alcohol alkoxylates especially C1Q to C18 such as to C15 alcohol ethoxylates; reaction products of PIBSA's with alkanolamines such as tri-ethanolamine; and polysorbate fatty acid esters, In particular, monoesters and esters of particularly unsaturated fatty acids such as polysorbate monooleic acid; sulfonic acid dispersants such as alkylarylsulfonic acids; or resin-containing components
第9頁 546370 五、發明說明⑹ ’ 着=:f醛樹脂分散劑以及乙稀—乙酸乙稀醋 刀H“使用時其典型含量係占溶劑配方之丄至4〇:,物L 1至3 0 %,及較佳1至2 0 %重量比。 ’°更常 額外添加劑例如流體耗損劑特別例如合 稀酿胺類、聚两稀《類、聚酿胺類及類似聚:如聚兩 也可作為黏度改良劑);防姓劑;去乳化劑;J分 清除劑及其它類似之添加物質含括於本發明使用乳 方。特別當使用其它添加劑時,可使用_或多 =釗配 如水溶性醇及丙醇,特別係用於於水存在下操劑例 /或可含括該添加劑之分散劑。 、糸統及 鲁 通常於產油井,含油岩層以及原油之溫度經一 圍溫度,典型係於50至150。〇 ,特別6〇至12〇1 :嗖過周 青烯及/或石油蠟於其岩層溫度以下之溫度沉積,祀圍、。瀝 係於前述範圍内或略低,特別係於4〇至U 〇 t之〜一通常 (I)化合物特別苯甲酸異丙酯為此等材料於中等。式 之較佳滚劑。知此較佳係於超過周圍溫度進行向溫度 加熱溶劑或却如於油井内接觸升高溫度之岩層二如畜意 劑性能。油管、油槽及精煉廠設備溫度通常^蕻=改良溶 溫度決定(常關聯進給溫度)。 ㈢預定操作 處理設備可為油管例如油井構造中的油管,勺 殼之内部=:t路包括油井頭管、海底油管外 路;或油槽例如油分離器(用以分離氣相、二及精煉薇管 脂相);貯軺,特別接近油井頭以及位於接』二含樹 及精煉設備"稀及/或石油壤沉積物去除;溶;Page 9 546370 V. Description of the invention 着 =: f aldehyde resin dispersant and ethylene-acetic acid vinegar knife H "The typical content when used is accounted for 丄 to 40 :, L 1 to 3 0%, and preferably 1 to 20% by weight. '° More often additional additives such as fluid loss agents, such as polyamines, polyamines, polyamines and similar polymers: such as polyamines also Can be used as viscosity improver); anti-surname agent; de-emulsifier; J-point scavenger and other similar additives are included in the use of milk formula in the present invention. Especially when other additives are used, _ or more = can be used as water Soluble alcohols and propanols are especially used as dispersants in the presence of water and / or dispersants that can include the additive. The sintering system and the lubricating oil are usually used in oil producing wells, oil-bearing rock formations, and crude oil. It is between 50 and 150. 0, especially 60 to 120. It is deposited at a temperature below the temperature of its rock formation, and the sacrifice is within the aforementioned range or slightly lower, especially A range of 40 to U 0 ~ ~ usually a (I) compound especially isopropyl benzoate for this purpose The material is medium. The formula is better. It is known that it is better to heat the solvent to the temperature above the surrounding temperature or to contact the rock formation with elevated temperature in the oil well. Secondly, the performance is like animal husbandry. Oil pipes, oil tanks and refineries. The temperature of the equipment is usually ^ 蕻 = determined by the improvement of the melting temperature (often related to the feed temperature). ㈢The predetermined operation processing equipment can be an oil pipe such as an oil pipe in an oil well structure. The inside of the scoop shell =: t includes the oil well head pipe and the subsea oil pipe outer road. Or oil tanks such as oil separators (to separate the gas phase, secondary and refined wicker lipid phases); storage tanks, particularly close to oil wellheads and located next to the two trees and refining equipment " thin and / or petroleum soil deposits Remove
第10頁 546370 五、發明說明⑺ 導入接觸沉積物,若有所需提供溶劑之循環或攪動,以_及 由設備去除軟化的、溶解的或分散的沉積物。於貯槽及其 它精煉處理所在位置,使用溶劑去除貯槽底餾分之優點無 需開啟貯槽進行機械清潔。貯槽内容物、貯槽底餾分及/ 或溶劑可經加熱而輔助溶解,焦油狀的固體貯槽底餾分分 散入溶劑内且通常加至原油流接受進一步精煉處理。 本發明包括一種處理油貯槽、油槽或油精煉管路,俾去 除歷青烯及/或石油堰沉積物之方法,其中包括如上定義 之式(I)化合物之處理材料於或鄰近瀝青烯及/或石油蠟沉 積物所在位置被導入貯槽、油槽或管路内,以及隨後軟_化 的、分散的或溶解的瀝青烯及/或石油蠟由貯槽、油槽或 管路去除。 特別於油井,習知技術包括預防性施用溶劑,溶劑選擇 性包括分散劑,其目的係為了防止瀝青烯及/或石油蠟的 絮凝及沉積。此等方法通常包含例如使用毛細管將處理物 質向下泵送入油井内,或藉滑溜流進行連續處理。如此於 可能發生沉積的位置舖設一薄層處理材料,而可有效防止 於管路及流動管線的絮凝與沉積。此種材料於接近油井鑽 孔區例如產油岩層本身内部防止沉積較為無效。此種情況 下,處理材料需置於岩層内,於岩層内例如經由將處理材 料擠入岩層而抑制固體沉積。 根據本發明包括一種處理油井俾去除瀝青烯及/或石油 蠟沉積物之方法,其中包括如上定義之式(I )化合物之溶 劑導入油井-内於表面上之沉積物或其附近或於岩層。Page 10 546370 V. Description of the invention ⑺ Introduce contact deposits, if necessary, provide circulation or agitation of solvent, and remove softened, dissolved or dispersed deposits by equipment. The advantage of using a solvent to remove the bottom fraction of the storage tank at the location of the storage tank and other refining processes does not require the storage tank to be opened for mechanical cleaning. Tank contents, tank bottoms, and / or solvents can be heated to assist dissolution, and tar-like solid tank bottoms are dispersed into the solvent and are usually added to the crude oil stream for further refining. The present invention includes a method for treating an oil storage tank, an oil tank or an oil refining pipeline to remove alventene and / or petroleum weir deposits, which includes a treatment material of a compound of formula (I) as defined above at or near asphaltene and / Or the location of the petroleum wax deposit is introduced into the storage tank, oil tank or pipeline, and the subsequently softened, dispersed or dissolved asphaltene and / or petroleum wax is removed from the storage tank, oil tank or pipeline. Especially in oil wells, conventional techniques include preventive application of solvents, and solvent selectivity includes dispersants, the purpose of which is to prevent flocculation and deposition of asphaltenes and / or petroleum waxes. These methods typically include, for example, the use of a capillary tube to pump down the processing material into an oil well, or continuous processing by slipstreaming. Laying a thin layer of processing material in the place where deposition may occur in this way can effectively prevent flocculation and deposition in pipelines and flow pipelines. This type of material is less effective in preventing sedimentation in areas near the boreholes of oil wells, such as the oil-producing formations themselves. In this case, the treatment material needs to be placed in a rock formation, and solid deposition is suppressed in the rock formation, for example, by squeezing the treatment material into the rock formation. A method according to the present invention includes treating an oil well to remove asphaltenes and / or petroleum wax deposits, which comprises introducing a solvent of a compound of formula (I) as defined above into an oil well-a deposit on or near the surface or in a rock formation.
第11頁 546370 五、發明說明(8) 本發明進一步包括一種處理油井俾防止瀝青烯類及/或 石油蝶類沉積之方法,其中包括如上定義之式(I )化合物 之處理材料流被導入油井内之一個位置,特別導引至表面 上或岩層内,此處預期發生沉積,藉此於瀝青烯及/或石 油墩沉積於表面或岩層之前將遞青稀及/或石油墙帶離。 下列實例舉例說明本發明。除非另行載明,否則全部份 數及百分比係以重量計。 實例1 , 史坎坦(S c a m p t ο n ) C 4原油添加至己烧而沉積遞青稀(己 烷溶解瀝青烯安定作用樹脂),移開上溶劑層,讓殘餘g m 烷蒸發而獲得瀝青烯呈黏稠液態殘餘物。添加5. 2克苯甲 酸異丙酯溶劑至〇 . 〇 4 8克瀝青烯,於周圍溫度經數分鐘 後,實質上全部瀝青烯皆已經溶解(少數極小的瀝青烯粒 子於溶液中仍然可見)。溶解度估值(最低值)計算得約為 0 . 8 5 %重量比。 實例1 a 於分開實聲中,瀝青烯係如實例1所述製備,其溶解度 如實例1所述於各種溶劑進行評估。溶劑為苯曱酸乙酯、 苯甲酸異丙g旨、苯甲酸2-乙基己酯、苯甲酸壬酯、苯甲酸 異丙自旨及苯曱酸壬醋之3 : 1重量比混合物、(混合q 2 / q 3烧 基)笨曱酸酯及苯甲酸異硬脂酯。各例中,大部分瀝青烯 皆溶解,但少數極小型粒子仍然於溶液中維持可見。 實例2 約0 . 025克瀝青烯(如實例1所述獲得)塗抹於經過稱重的Page 11 546370 5. Description of the invention (8) The present invention further includes a method for treating oil wells to prevent the deposition of asphaltenes and / or petroleum butterflies, wherein the treatment material stream including the compound of formula (I) as defined above is introduced into the oil well A location inside, specifically directed to the surface or rock formation, where deposition is expected to occur, thereby taking away the thinning and / or petroleum wall before asphaltenes and / or petroleum mounds are deposited on the surface or rock formation. The following examples illustrate the invention. Unless otherwise stated, all parts and percentages are by weight. Example 1: Scampan oil was added to the sintered oil to deposit dilute dilute (hexane dissolves asphaltene stabilization resin), the upper solvent layer was removed, and the residual gm alkane was evaporated to obtain asphaltene. It was a viscous liquid residue. Add 5.2 grams of isopropyl benzoate solvent to 0.08 grams of asphaltene. After a few minutes at ambient temperature, substantially all of the asphaltene has been dissolved (a few tiny asphaltene particles are still visible in the solution) . The solubility estimate (lowest value) was calculated to be approximately 0.85% by weight. Example 1a In a separate real sound, asphaltene was prepared as described in Example 1, and its solubility was evaluated in various solvents as described in Example 1. The solvent is ethyl benzoate, isopropyl benzoate, 2-ethylhexyl benzoate, nonyl benzoate, isopropyl benzoate, and 3: 1 by weight mixture of nonyl benzoate, ( Mix q 2 / q 3 alkyl) benzoate and isostearyl benzoate. In each case, most of the asphaltenes were dissolved, but a few very small particles remained visible in the solution. Example 2 Approximately 0.025 grams of asphaltene (obtained as described in Example 1) was applied to a weighed
第12頁 546370 五、發明說明(9) 5厘米X 1厘米矩形軟鋼片上,且置於稱重玻璃瓶内,然後 再度稱重,由差值算出遞青稀含量υ加入約2毫升溶劑(準 確稱重),將瓶密封以及密封瓶放置於移動中的滾輪上, 故金屬片於周圍溫度下恆常被溶劑覆蓋約半小時。瀝青烯 完全由金屬片移開,瀝青烯於溶劑之有效最低溶解度為 1. 3 %。使用二甲苯作溶劑獲得類似結果。 實例2 a 於分開實驗,使用實例1 a列舉之溶劑重複實例2。各例 中,溶劑可由金屬片去除全部瀝青烯。 實例3 一 使用約0. 1 8克瀝青烯及約0, 5毫升苯甲酸異丙酯重複實 例2。; >T劑仍可由金屬片去除全部瀝青烯。 f ί·Η ;ί a 於一分開實驗中,使用不同數量重複實例3 : 0 . 4克瀝青 烯及1毫升溶劑,及實例1 a列舉的溶劑。各例中,於滾軋 結束時大部分瀝青烯皆被去除,但有小量維持黏著於金屬 面。殘餘物無法定量測量,但目測觀視金屬片,提示本試 驗之溶劑評比(由最佳至最差): 苯曱酸乙酯〉苯甲酸壬酯〉苯甲酸2-乙基己酯〉苯曱酸異 丙酯與苯甲酸壬酯之3 : 1重量比混合物〉苯曱酸異丙酯〉苯 甲酸(混合C12/C13烷基)酯〉苯甲酸異硬脂酯。 實例4 測量白軟石蠟[熔點4 9至5 9 °C ]於苯曱酸異丙酯溶解度 。於周圍溫度,蠟溶解度為低(低於1 % ),但溫熱至5 0至6 0Page 12 546370 V. Description of the invention (9) 5 cm X 1 cm rectangular soft steel sheet, placed in a weighing glass bottle, and then weighed again, calculate the dilute dilute content from the difference and add about 2 ml of solvent (accurate Weighing), the bottle is sealed and the sealed bottle is placed on a moving roller, so the metal piece is always covered with the solvent at the ambient temperature for about half an hour. Asphaltene is completely removed from the metal sheet. The effective minimum solubility of asphaltene in the solvent is 1.3%. Similar results were obtained using xylene as the solvent. Example 2a In a separate experiment, Example 2 was repeated using the solvents listed in Example 1a. In each case, the entire asphaltene was removed from the metal sheet by the solvent. Example 3-Example 2 was repeated using about 0.18 g of asphaltene and about 0.5 ml of isopropyl benzoate. ; ≫ T agent can still remove all asphaltene from the metal sheet. f ί · Η; ί a In a separate experiment, Example 3: 0.4 g of asphaltene and 1 ml of solvent were repeated using different amounts, and the solvents listed in Example 1 a. In each case, most of the asphaltene was removed at the end of rolling, but a small amount remained adhered to the metal surface. The residue cannot be measured quantitatively, but visual inspection of the metal sheet suggests the solvent evaluation (from best to worst) of this test: ethyl benzoate> nonyl benzoate> 2-ethylhexyl benzoate> benzene 3: 1 weight ratio mixture of isopropyl ester and nonyl benzoate> isopropyl benzoate> isobenzoate (mixed C12 / C13 alkyl) ester> isostearyl benzoate. Example 4 Measurement of the solubility of white soft paraffin [melting point 49 to 59 ° C] in isopropyl phenylacetate. Wax solubility is low (less than 1%) at ambient temperature, but warm to 50 to 60
第13頁 546370 五、發明說明(ίο) °C時,可溶解大於60%重量比蠟(基於溶劑)。 _ 實例4 a 於分開實驗,重複實例4而評比白軟石蠟於實例1 a列舉 溶劑之溶解度。各例中,溶解度於周圍溫度顯然較低,但 於6 0 °C大於6 0 %重量比蠟可溶解於各溶劑。 實例5 經由將白軟石蠟塗抹於金屬片表面,經過稱重之金屬片 塗覆以實例4所述蠟,使用實例2所述方法測試蠟被苯曱酸 異丙酯之去除情形。蠟含量約占溶劑之1 0 %重量比。於周 圍溫度,小量蠟被去除而獲得混濁溶液,但於5 9 °C全部_蠟 皆易由金屬片表面被去除。 實例5 a 於分開實驗t ,使用白軟石蠟及實例1 a列舉之溶劑重複 實例5。各溶劑於周圍溫度可去除全部蠟而形成混濁溶液 。目測檢驗混濁程度,提示本試驗中溶劑之排名為(由最 佳至最差): 苯曱酸異硬脂酯〜苯甲酸異硬脂酯〉苯曱酸壬酯〜苯甲 酸2-乙基己酯〉苯曱酸乙酯〜苯曱酸異丙酯〜笨曱酸異丙 酯與苯甲酸壬酯之3 : 1重量比混合物。Page 13 546370 V. Description of the invention (°) At ° C, it can dissolve more than 60% by weight of wax (based on solvent). _ Example 4 a In a separate experiment, Example 4 was repeated to evaluate the solubility of the white soft paraffin in Example 1 a. In each case, the solubility is obviously lower at ambient temperature, but at 60 ° C greater than 60% by weight wax can be dissolved in various solvents. Example 5 The white soft paraffin was applied to the surface of a metal sheet, and the weighed metal sheet was coated with the wax described in Example 4. The method described in Example 2 was used to test the removal of the wax by isopropyl phenylacetate. The wax content is about 10% by weight of the solvent. At the ambient temperature, a small amount of wax was removed to obtain a turbid solution, but at 5 9 ° C all waxes were easily removed from the surface of the metal sheet. Example 5a In a separate experiment t, Example 5 was repeated using white soft paraffin and the solvents listed in Example 1a. Each solvent can remove all waxes at ambient temperature to form a turbid solution. Visual inspection of the degree of turbidity indicated that the ranking of the solvents in this test was (from best to worst): isostearyl benzoate ~ isostearyl benzoate> nonyl benzoate ~ 2-ethylhexyl benzoate Esters> Ethyl Phenylacetate ~ Isopropyl Phenylacetate ~ Isopropyl Benzoate and Nonyl Benzoate in a 3: 1 weight ratio mixture.
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發明專利說明書 發明名稱 發明人 申請人 中文 "|||^積瀝青賊石油it、或防止、或 或石油堪沉積於油處理設 英文 ppfv™t?\ipRE^ 0R PEtr〇LEUM WAXES DEPOSITED IN, OR S早喆tNS化λ%。?ΚΙβΠτΙΝ&^ΤΗΕ DEi>0SITI0N 0F ASPHALTENES 0R PETROLEUM WAXES IN, OIL TREATMENT EQUIPMENT 姓名 (中文) 1.德倫西寇克斯 " 2·尽爾葛倫格 3.愛德華喬治史柯維爾 姓名 (英文) Fterence COX --- 2. NEIL GRAINGER 3. EDWARD GEORGE SCOVELL 國籍 "Γ英國2.英國3.英國 "" 住、居所 姓名 (名稱) (中文) 111岳f恩I?佛頓文路25號 ?· S S塞念255费S 5f克市康威葛洛芙路3號 3·夬國雄、德斯柏郡格雷安頓市史暑多槐聖路27號 ΤΓ英商卜内門洋鹼公司 ----- 姓名 (名稱) (英文) 1. IMPERIAL CHEMICAL INDUSTRIES PLC 國籍 1.英國 彳主、居所 (事務所) 1·英國偷敦巾曲兩一區米爾本卜内門大廈 代表人 姓名 (中文) 1.約翰G.格拉漢 _ 代表人 姓名 (英文) Γ·—JOHN G. GRAHAM '- 第1頁Invention Patent Specification Invention Name Inventor Applicant Chinese " ||| ^ Accumulating Asphalt Thief Petroleum It, or Preventing Or Or Petroleum Depositing In Oil Treatment Equipment pfv ™ t? \ IpRE ^ 0R PEtr〇LEUM WAXES DEPOSITED IN, OR S was early tNS λ%. ? ΚΙβΠτΙΝ & ^ ΤΗΕ DEi > 0SITI0N 0F ASPHALTENES 0R PETROLEUM WAXES IN, OIL TREATMENT EQUIPMENT Name (Chinese) 1. Deron Sycox " 2 · Geer Grenger 3. Edward George Scowell Name (English) Fterence COX --- 2. NEIL GRAINGER 3. EDWARD GEORGE SCOVELL Nationality " Γ United Kingdom 2. United Kingdom 3. United Kingdom " " Name of Residence (Name) (Chinese) 111 Yue Fen I? Futton Way 25 No. · SS Seinian 255 fee S 5f grams of No. 3 Conway Grove Road, City of China 3 · Guoxiong Xiong, 27, Huaihuan Sheng Road, Shi'an County, Dean Park County ---- Name (Name) (English) 1. IMPERIAL CHEMICAL INDUSTRIES PLC Nationality 1. British Owner, Residence (Office) 1. Representative Name of Millburn Bunnemen Building ) 1. John G. Graham _ Name of Representative (English) Γ · —JOHN G. GRAHAM '-Page 1
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GBGB0007830.3A GB0007830D0 (en) | 2000-03-31 | 2000-03-31 | Maintenance of oil production and refining equipment |
US20503100P | 2000-05-18 | 2000-05-18 |
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AR (1) | AR028524A1 (en) |
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EA (1) | EA004278B1 (en) |
MX (1) | MXPA02009674A (en) |
NO (1) | NO20024638L (en) |
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US20030213747A1 (en) * | 2002-02-27 | 2003-11-20 | Carbonell Ruben G. | Methods and compositions for removing residues and substances from substrates using environmentally friendly solvents |
EA201290662A1 (en) * | 2010-02-24 | 2013-05-30 | Родиа Оперейшнс | SYSTEMS AND METHODS FOR ASSESSING INHIBITORS OF ASPHALTEN SURFACE |
US9106194B2 (en) | 2010-06-14 | 2015-08-11 | Sony Corporation | Regulation of audio volume and/or rate responsive to user applied pressure and related methods |
MX337888B (en) * | 2010-06-28 | 2016-03-09 | Geo Estratos S A De C V | Asphaltene-controlling additive compound for oil. |
CN102321464B (en) * | 2011-07-15 | 2013-04-24 | 中国石油天然气股份有限公司 | Corrosion and scale inhibitor for oil well in high water-cut period |
DK2869704T3 (en) | 2012-07-04 | 2018-10-29 | Marel Meat Bv | Carcass transport system or parts of slaughtered four-legged animals |
US9921205B2 (en) | 2012-11-13 | 2018-03-20 | Chevron U.S.A. Inc. | Method for determining the effectiveness of asphaltene dispersant additives for inhibiting or preventing asphaltene precipitation in a hydrocarbon-containing material subjected to elevated temperature and presssure conditions |
CN105339585A (en) * | 2013-06-27 | 2016-02-17 | 国际壳牌研究有限公司 | Remediation of asphaltene-induced plugging of wellbores and production lines |
US10759990B2 (en) | 2014-01-16 | 2020-09-01 | Wilmar Trading Pte Ltd. | Use of olefinic ester compositions in oil and gas fields |
US11053430B2 (en) | 2014-01-16 | 2021-07-06 | Wilmar Trading Pte Ltd. | Olefinic ester compositions and their use in stimulating hydrocarbon production from a subterranean formation |
US10858573B2 (en) * | 2014-01-16 | 2020-12-08 | Wilmar Trading Pte Ltd | Olefinic ester compositions and their use as cleaning agents |
US10081760B2 (en) | 2014-01-16 | 2018-09-25 | Elevance Renewable Sciences, Inc. | Olefinic ester compositions and their use in stimulating hydrocarbon production from a subterranean formation |
US10907473B2 (en) | 2017-11-14 | 2021-02-02 | Chevron U.S.A., Inc. | Low volume in-line filtration methods for analyzing hydrocarbon-containing fluid to evaluate asphaltene content and behavior during production operations |
US20240117238A1 (en) | 2022-09-28 | 2024-04-11 | Championx Llc | Extended release asphaltene inhibitor composition |
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US2786085A (en) * | 1952-08-20 | 1957-03-19 | Universal Oil Prod Co | Solvent extraction process applied to feed stocks of high boiling points |
US3693720A (en) * | 1971-01-29 | 1972-09-26 | Exxon Research Engineering Co | Crude oil recovery method using a polymeric wax inhibitor |
US5425422A (en) * | 1993-09-21 | 1995-06-20 | Noranda Inc. | Process for removing and preventing near-wellbore damage due to asphaltene precipitation |
US6187172B1 (en) * | 1999-05-24 | 2001-02-13 | Marathon Oil Company | Viscosity reduction of crude oils and residuums |
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