CN115044358B - Environment-friendly paraffin removal and prevention agent and preparation method thereof - Google Patents
Environment-friendly paraffin removal and prevention agent and preparation method thereof Download PDFInfo
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- CN115044358B CN115044358B CN202210868557.1A CN202210868557A CN115044358B CN 115044358 B CN115044358 B CN 115044358B CN 202210868557 A CN202210868557 A CN 202210868557A CN 115044358 B CN115044358 B CN 115044358B
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- 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
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
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Abstract
The invention discloses an environment-friendly paraffin remover and inhibitor, which is prepared from the following raw materials in parts by weight: 70-99 parts of paraffin remover, 1-30 parts of penetrating agent and 1-10 parts of paraffin inhibitor; the paraffin remover is at least one of limonene, cyclopentadiene, jasmone, propyl lactone and butyl lactone; the wax inhibitor is prepared by copolymerization of monomer ethyl acrylate, acrylate and maleic anhydride under the action of an initiator; the penetrating agent is polyether surfactant; the penetrating agent is selected from at least one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether and fatty amine polyoxyethylene ether. The paraffin removal and prevention agent is simple in preparation process, does not contain organic chlorine, carbon disulfide, carbon tetrachloride and benzene series, has efficient paraffin removal and prevention effects, is safe to human bodies and environment, does not cause oil refining catalyst poisoning, and can avoid the environmental protection problem while efficiently removing paraffin in oil wells.
Description
Technical Field
The invention relates to the technical field of oilfield exploitation, in particular to an environment-friendly paraffin removal and prevention agent and a preparation method thereof.
Background
Most oil fields in China are wax-containing crude oil. Before well development, the wax was completely dissolved in the crude oil. In the process of oil well exploitation, crude oil flows into the bottom of a well from an oil layer and then is lifted from the bottom of the well, and with the gradual reduction of temperature and pressure, paraffin is crystallized and separated out, and is aggregated and coagulated to adhere to the metal surface of an oil well facility, so that the normal production of a normal oil well is influenced. The wax blocks formed are mainly paraffin wax and microcrystalline wax, and most of the paraffin wax mainly contains normal paraffin. The wax deposition of the oil well is mainly influenced by the wax content of crude oil, pressure, dissolved gas amount, wellbore lifting temperature difference and pipe wall properties, wherein the high crude oil content is an important internal cause for wax deposition. Therefore, the wax precipitation problem of the existing high wax content oil well is treated by adopting physical, chemical and biological modes, and the chemical wax removal and prevention is widely applied due to simple process and low cost. However, the common solvents with good paraffin removal performance mainly comprise substances such as carbon disulfide, carbon tetrachloride, benzene, toluene, gasoline, petroleum ether and the like, and the solvents have the problems of high toxicity, low flash point, easiness in causing oil refining catalyst poisoning and the like. Diesel oil or white oil is also used as a solvent, but the wax-dissolving rate of the diesel oil is low. The industrial white oil also has the problem of sulfur. Therefore, it becomes necessary to research an environmentally friendly, safe and efficient paraffin removal and prevention agent.
Disclosure of Invention
Aiming at the problems of high toxicity, low flash point, easy oil refining catalyst poisoning and the like of the existing chemical paraffin removal and prevention agent, the invention provides an environment-friendly paraffin removal and prevention agent.
The environment-friendly wax removing and preventing agent provided by the invention is prepared from the following raw materials in parts by weight: 70 to 99 parts of paraffin remover, 1 to 30 parts of penetrating agent and 1 to 10 parts of wax inhibitor. Adding the paraffin remover, the penetrating agent and the paraffin inhibitor into a reaction vessel, and uniformly stirring at 25-40 ℃ to obtain the environment-friendly paraffin remover and paraffin inhibitor.
The paraffin remover is at least one of limonene, cyclopentadiene, jasmone, propyl lactone and butyl lactone; are all environment-friendly organic solvents.
The penetrating agent is polyether surfactant. Preferably at least one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether and fatty amine polyoxyethylene ether.
The wax inhibitor is prepared by copolymerization of monomer ethyl acrylate, acrylic ester and maleic anhydride under the action of an initiator. The vinyl acid ester is selected from one of vinyl acetate, vinyl propionate, vinyl butyrate and vinyl versatate. The acrylate is selected from one of methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, 2-methyl methacrylate, 2-ethyl methacrylate and behenyl acrylate. The initiator is azobisisobutyronitrile or benzoyl peroxide.
The preparation method of the wax inhibitor comprises the following steps: adding ethyl acrylate, acrylic ester and maleic anhydride into a three-neck flask according to the molar ratio of 1 (1-10): 1, adding a toluene solvent, heating to 60 ℃ to completely dissolve the ethyl acrylate, introducing nitrogen, stirring, heating to 90 ℃, carrying out constant-temperature reflux reaction for 7 hours, adding an initiator with the mass percentage concentration of 0.5-2% for 4 times during the reaction, and drying and grinding after the reaction is finished to obtain the wax-proofing agent. The chemistry prevailing in the polymerization is as follows, the main product obtained being a terpolymer.
In addition to the terpolymers described above, small amounts of other polymers may also be present in the product of the polymerization reaction. In the present invention, a mixture of a plurality of polymers is directly used as an anti-wax agent without purification treatment after the polymerization reaction is completed. Wherein, the core component playing the wax-proof role is terpolymer.
Compared with the prior art, the invention has the advantages that:
the wax removing and preventing agent of the invention selects the environment-friendly organic solvent as the wax removing agent, not only has the characteristic of high wax dissolving rate, but also does not contain components which are easy to cause catalyst poisoning, such as organic chlorine, carbon disulfide, carbon tetrachloride, benzene series and the like. The wax inhibitor is prepared by copolymerization of monomer ethyl acrylate, acrylate and maleic anhydride under the action of an initiator. The nonpolar long carbon chain on the copolymer molecule has a structure similar to that of the paraffin molecule, can be combined with the paraffin molecule to form eutectic, and has an obvious difference structure with the paraffin molecule to prevent the combination of wax crystals, so that the wax crystal form generates distortion deformation, and the wax crystal is not beneficial to growth and aggregation, thereby exerting the wax-proof effect.
The paraffin removal and prevention agent is used for removing wax blockage formed by wax, colloid and asphaltene in oil well pipes and oil pipelines of oil fields, and has a certain paraffin precipitation prevention effect. Moreover, the wax removing and preventing agent has simple preparation process, high wax removing rate and wax preventing rate, is safe to human bodies and environment, cannot cause oil refining catalyst poisoning, and can avoid the environmental protection problem while efficiently removing and preventing wax of oil wells.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
A preparation method of an environment-friendly paraffin remover and inhibitor comprises the following steps:
step 1, preparing an anti-wax agent: weighing vinyl acetate, methyl acrylate and maleic anhydride according to a molar ratio of 1.
Step 2, weighing 3g of fatty alcohol-polyoxyethylene ether, 2g of alkylphenol ethoxylate and 5g of fatty acid-polyoxyethylene ether, and uniformly stirring and mixing to obtain a composite surfactant serving as a penetrating agent; and adding 2g of wax inhibitor into the penetrating agent, uniformly stirring, then adding 88g of limonene, and uniformly stirring at 40 ℃ to obtain the environment-friendly wax removing and preventing agent.
Example 2
A preparation method of an environment-friendly paraffin remover and inhibitor comprises the following steps:
step 1, preparing an anti-wax agent: the method comprises the following steps of weighing vinyl butyrate, eicosyl acrylate and maleic anhydride according to a molar ratio of 1.
Step 2: weighing 6g of fatty alcohol-polyoxyethylene ether, 6g of alkylphenol polyoxyethylene ether and 3g of fatty amine polyoxyethylene ether, and uniformly stirring and mixing to obtain a composite surfactant serving as a penetrating agent; and adding 5g of wax inhibitor into the penetrating agent, uniformly stirring, then adding 80g of cyclopentadiene, and uniformly stirring at 35 ℃ to obtain the environment-friendly wax removing and preventing agent.
Example 3
A preparation method of an environment-friendly paraffin remover and inhibitor comprises the following steps:
step 1, preparing an anti-wax agent: weighing vinyl propionate, 2-methyl methacrylate and maleic anhydride according to a molar ratio of 1.
Step 2, weighing 10g of fatty alcohol-polyoxyethylene ether, 7g of alkylphenol ethoxylates and 5g of fatty acid-polyoxyethylene ether, uniformly stirring to obtain a composite surfactant serving as a penetrating agent, adding 3g of paraffin inhibitor into the penetrating agent, uniformly stirring, adding 75g of jasmone, and uniformly stirring at 25 ℃ to obtain the environment-friendly paraffin removal and prevention agent.
Example 4
A preparation method of an environment-friendly paraffin remover and inhibitor comprises the following steps:
step 1, preparing an anti-wax agent: weighing vinyl propionate, 2-methyl methacrylate and maleic anhydride according to a molar ratio of 1.
Step 2, weighing 10g of fatty alcohol-polyoxyethylene ether, 7g of alkylphenol ethoxylates and 5g of fatty acid-polyoxyethylene ether, uniformly stirring to obtain a composite surfactant serving as a penetrating agent, adding 3g of paraffin inhibitor into the penetrating agent, uniformly stirring, adding 45g of propyl lactone and 30g of butyl lactone, and uniformly stirring at 40 ℃ to obtain the environment-friendly paraffin inhibitor.
Comparative example 1:
a preparation method of the paraffin removal and prevention agent comprises the following steps:
step 1, preparing an anti-wax agent: weighing vinyl acetate and methyl acrylate according to a molar ratio of 1.
Step 2, weighing 3g of fatty alcohol-polyoxyethylene ether, 2g of alkylphenol ethoxylate and 5g of fatty acid-polyoxyethylene ether, and uniformly stirring and mixing to obtain a composite surfactant serving as a penetrating agent; and adding 2g of wax inhibitor into the penetrating agent, uniformly stirring, then adding 88g of limonene, and uniformly stirring at 40 ℃ to obtain the environment-friendly wax removing and preventing agent.
Comparative example 2:
a preparation method of the paraffin removal and prevention agent comprises the following steps:
step 1, preparing an anti-wax agent: weighing vinyl acetate and maleic anhydride according to a molar ratio of 1.
Step 2, weighing 3g of fatty alcohol-polyoxyethylene ether, 2g of alkylphenol ethoxylate and 5g of fatty acid-polyoxyethylene ether, and uniformly stirring and mixing to obtain a composite surfactant serving as a penetrating agent; and adding 2g of wax inhibitor into the penetrating agent, uniformly stirring, then adding 88g of limonene, and uniformly stirring at 40 ℃ to obtain the environment-friendly wax removing and preventing agent.
Comparative example 3:
a preparation method of the paraffin removal and prevention agent comprises the following steps:
step 1, preparing an anti-wax agent: weighing methyl acrylate and maleic anhydride according to a molar ratio of 1.
Step 2, weighing 3g of fatty alcohol-polyoxyethylene ether, 2g of alkylphenol ethoxylate and 5g of fatty acid-polyoxyethylene ether, and uniformly stirring and mixing to obtain a composite surfactant serving as a penetrating agent; and adding 2g of wax inhibitor into the penetrating agent, uniformly stirring, then adding 88g of limonene, and uniformly stirring at 40 ℃ to obtain the environment-friendly wax removing and preventing agent.
Comparative example 4:
on the basis of example 1, the wax inhibitor is removed, and the corresponding preparation method comprises the following steps: weighing 3g of fatty alcohol-polyoxyethylene ether, 2g of alkylphenol ethoxylate and 5g of fatty acid-polyoxyethylene ether, and uniformly stirring and mixing to obtain a composite surfactant serving as a penetrating agent; 88g of limonene is added into the penetrating agent, and the mixture is stirred uniformly at 40 ℃ to obtain the paraffin remover and inhibitor.
Comparative example 5:
on the basis of example 1, 88g of limonene was replaced by 88g of white No. 3 as a solvent, and a paraffin remover and inhibitor was obtained.
Comparative example 6:
on the basis of example 1, 88g of limonene is replaced by 88g of 5# diesel oil as a solvent, and a paraffin removal and prevention agent is obtained.
The environmental-friendly paraffin removal and prevention agents prepared in examples 1 to 4 and the paraffin removal and prevention agents prepared in comparative examples 1 to 6 were used for measuring the paraffin dissolution rate of the product according to the test method in SY/T6300-2009 technical conditions for paraffin removal and prevention agents for oil recovery, and No. 56 to No. 58 paraffin. The test results are shown in Table 1.
TABLE 1 test result data
| Rate of wax dissolution (g/min) | Percent wax control (%) | |
| Example 1 | 0.0231 | 65 |
| Example 2 | 0.0194 | 52 |
| Example 3 | 0.0187 | 43 |
| Example 4 | 00166 | 37 |
| Comparative example 1 | 0.0227 | 34 |
| Comparative example 2 | 0.0213 | 29 |
| Comparison ofExample 3 | 0.0216 | 27 |
| Comparative example 4 | 0.0221 | 22 |
| Comparative example 5 | 0.0146 | 41 |
| Comparative example 6 | 0.0142 | 36 |
Compared with the conventional diesel oil or white oil, the environmental-friendly organic solvent (wax remover) adopted by the invention has better wax dissolving rate and higher wax prevention rate. Meanwhile, the wax removing and preventing agent obtained by using the copolymer of three monomers, namely the ethyl acrylate, the acrylic ester and the maleic anhydride, as the wax preventing agent has wax dissolving and preventing performances which are obviously superior to those of any two monomer polymers as the wax preventing agent.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. The environment-friendly paraffin remover and inhibitor is characterized by comprising the following raw materials in parts by weight: 70 to 99 parts of paraffin remover, 1 to 30 parts of penetrant and 1 to 10 parts of wax inhibitor; the paraffin remover is at least one of cyclopentadiene, jasmone, propyl lactone and butyl lactone;
the wax inhibitor is prepared by copolymerization of monomer ethyl acrylate, acrylate and maleic anhydride under the action of an initiator; the preparation method comprises the following steps: adding ethyl acrylate, acrylic ester and maleic anhydride into a three-neck flask according to the molar ratio of 1 (1 to 10): 1, adding a toluene solvent, heating to 60 ℃ to completely dissolve the ethyl acrylate, introducing nitrogen, stirring, heating to 90 ℃, carrying out constant-temperature reflux reaction for 7 hours, adding an initiator with the mass percentage concentration of 0.5-2% for 4 times during the reaction, and drying and grinding after the reaction is finished to obtain the wax-proofing agent;
the vinyl acid ester is selected from one of vinyl acetate, vinyl propionate and vinyl butyrate;
the acrylic ester is selected from one of methyl acrylate, ethyl acrylate, butyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate;
the penetrating agent is polyether surfactant.
2. The environmentally friendly paraffin remover and inhibitor of claim 1, wherein the penetrating agent is at least one selected from fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, fatty acid-polyoxyethylene ether, and fatty amine-polyoxyethylene ether.
3. The environmentally friendly paraffin remover and inhibitor of claim 1, wherein the initiator is azobisisobutyronitrile or benzoyl peroxide.
4. The preparation method of the environment-friendly paraffin remover and inhibitor as claimed in any one of claims 1 to 3, wherein the paraffin remover, the penetrating agent and the paraffin inhibitor are added into a reaction vessel and uniformly stirred at 25-40 ℃ to obtain the environment-friendly paraffin remover and inhibitor.
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Citations (3)
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| CN101240702A (en) * | 2007-02-09 | 2008-08-13 | 钜力集团有限公司 | Oil layer coagulating type oil reservoir mining method |
| CN105086976A (en) * | 2015-08-25 | 2015-11-25 | 中国石油化工股份有限公司 | Efficient wax inhibitor for oilfields |
| CN107619455A (en) * | 2016-07-15 | 2018-01-23 | 中国石油天然气集团公司 | Comb polymer for pour point depressant for crude oil and preparation method thereof, application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101265800B (en) * | 2007-03-13 | 2012-07-25 | 李向东 | Oil layer wax-condensing type oil reservoir mining method |
| CN104086687A (en) * | 2014-06-27 | 2014-10-08 | 中国石油大学(华东) | Preparation method of crude oil macromolecular wax-proofing agent |
| MX2017000648A (en) * | 2014-07-15 | 2017-04-27 | Sasol Performance Chemicals Gmbh | Compositions and methods for controlling paraffin and asphaltene problems in wells. |
| CN105567201A (en) * | 2014-10-09 | 2016-05-11 | 中国石油天然气股份有限公司 | Oil well oil-based wax removing agent |
| CN105419759B (en) * | 2015-12-24 | 2018-05-04 | 陕西延安石油天然气有限公司 | A kind of high-efficiency environment friendly oil-base paraffin remover |
| CN108441199A (en) * | 2018-03-23 | 2018-08-24 | 北京捷贝通石油技术股份有限公司 | A kind of environment-friendly highly efficient heavy crude thinner |
| US20200369944A1 (en) * | 2019-05-21 | 2020-11-26 | Plus5, Inc. | Method and product for paraffin and asphaltenes inhibiting |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240702A (en) * | 2007-02-09 | 2008-08-13 | 钜力集团有限公司 | Oil layer coagulating type oil reservoir mining method |
| CN105086976A (en) * | 2015-08-25 | 2015-11-25 | 中国石油化工股份有限公司 | Efficient wax inhibitor for oilfields |
| CN107619455A (en) * | 2016-07-15 | 2018-01-23 | 中国石油天然气集团公司 | Comb polymer for pour point depressant for crude oil and preparation method thereof, application |
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