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

Abstract

The deposition of asphaltenes and/or petroleum waxes can be inhibited and/or asphaltenes and/or petroleum waxes can be removed from a well, pipe or vessel by contacting the asphaltene and/or petroleum wax or the well pipe or vessel adjacent a location where deposition of asphaltene and/or petroleum wax is expected, with a solvent including at least one compound of the formula (I): R1-(AO)n-OOC-(CH2)m-Ph-(R2)p, where R1 is a C1 to C20 hydrocarbyl group; AO is an alkyleneoxy group and may vary along the (poly)alkyleneoxy chain; n is 0 or from 1 to 100; m is 0, 1 or 2; and Ph is a phenyl group, which may be substituted with groups (R2)p where each R2 is independently a C1 to C4 alkyl or alkoxy group; and p is 0, 1 or 2, and subsequently removing the solvent with softened, dissolved or dispersed asphaltenes and/or petroleum waxes from the well, pipe or vessel.

Description

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

546370

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: 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

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.

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 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

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

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.

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

Page 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

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.

Page 14 546370

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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

Claims (1)

546 Donkey Office k 901 06069 91. 11 1 year B month month month B Jli positive 6 patents _ 1 · A method for removing deposited asphaltene or petroleum wax, or preventing or inhibiting the dilution of asphalt or petroleum radon from A method of oil treatment equipment comprising contacting an oil well, tubing or oil tank contained in an oil treatment equipment adjacent to an asphaltene and / or petroleum wax deposition site with an asphaltene and / or petroleum wax, the solvent including at least A compound of formula (I): (I R1- (AO) n-OOC- (CH2) m-Ph- (R2) I where R1 is q to (^ alkyl); A 0 is an alkyleneoxy group, and may be (Poly) alkyleneoxy chain changes; η is 0 or 1 to 1 0 0; in is 0, 1 or 2; and Ph is phenyl, which may be substituted by (R2) p group; where each R2 is q To (: 4 alkyl or alkoxy; and p is 0, 1 or 2; and subsequent removal of solvents with softened, dissolved or dispersed asphalt dilute and / or petroleum fibers from oil wells, tubing or tanks. 2 . For the method of the scope of patent application, item 1, where m, η and p are all 0. 3. For the method of the scope of patent application item 1 or 2, where R1 is C3 to C5 branched alkyl groups. Wherein the solvent is or includes R1 is C8 to (: 2 {) of the asphaltene and / or 4. The method according to the first or second scope of the patent application, including isopropyl phenylacetate. 5. If the method of applying for the scope of the patent application item 1 or 2 and / or unsaturated alkyl or alkenyl group. 6. If the method of applying for the scope of the patent application item 1 or 2 petroleum can be exposed to the solvent above ambient temperature. O: \ 69 \ 69916-911115.ptc page 16 546370 _ case number 90106069_1 I 丨 month day amendment_ VI. Patent application scope 7. If the method of the first or second patent scope is requested, the solvent includes a Asphalt thinner and / or petroleum wax dispersant. 8. The method according to item 1 or 2 of the scope of patent application, which is used to treat oil storage 漕, container or oil refining pipeline 沥青 to remove asphaltene and / or petroleum wax deposits, wherein one kind includes the formula as defined above ( I) The solvent of the compound is introduced into a tank, container, or pipeline at or near the asphaltene and / or petroleum wax deposition location, and the softened, dissolved, or dispersed asphalt is subsequently removed from the tank, container, or pipeline by thinning and / or Petroleum fiber. 9. The method according to item 1 or 2 of the Chinese patent, which is used to treat oil wells to remove asphaltene and / or petroleum wax deposits, and a solvent including a compound of formula (I) as defined above is introduced into the oil well at Surface or rock formation deposits, or nearby, and subsequent removal of softened, dispersed, or dissolved turbid and / or petroleum soils from the surface or rock formation. 10. The method according to item 1 or 2 of the scope of patent application, which is used to treat oil wells to inhibit or prevent asphaltene and / or petroleum wax deposits, including the solvent flow of compounds of formula (I) as defined above. As far as the deposition is expected, especially on the surface or in the rock formation, the asphaltene and / or petroleum wax is taken away before the asphaltene and / or petroleum wax is deposited on the surface or rock formation. O: \ 69 \ 69916-911115.ptc Page 17