CN110437371A - A kind of quadripolymer oil soluble crude oil pour-point depressant and preparation method - Google Patents
A kind of quadripolymer oil soluble crude oil pour-point depressant and preparation method Download PDFInfo
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- CN110437371A CN110437371A CN201910799582.7A CN201910799582A CN110437371A CN 110437371 A CN110437371 A CN 110437371A CN 201910799582 A CN201910799582 A CN 201910799582A CN 110437371 A CN110437371 A CN 110437371A
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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
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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
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- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
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Abstract
The present invention relates to a kind of preparation methods of pour point depressant for crude oil.The pour-point depressant first passes through esterification and obtains octadecyl methacrylate, and then four kinds of octadecyl methacrylate, maleic anhydride, styrene, acrylamide monomer polymerizations are made by way of causing polymerization under nitrogen protection again.The polymer molecular weight matches with the wax in crude oil, can be very good the growth aggregation for inhibiting wax crystalline substance, to reduce the condensation point of crude oil, improves the mobility of crude oil.The raw material sources of the pour-point depressant are extensive, and synthesis technology is simple, at low cost, and condensation point of crude oil can be significantly reduced under seldom dosage.
Description
Technical field
The present invention relates to a kind of preparation methods of pour point depressant for crude oil, belong to oilfield chemical auxiliary field.
Background technique
The transport of pour point depressant for crude oil at home mainly has freighter, tank truck and pipeline transportation, wherein with being most widely
Pipeline transportation.After nineteen sixty, pour-point depressant has been used in oil extraction and pipeline transportation suffers, and effect is pretty good.After 1970
China starts to apply homemade pour-point depressant in Daqing oil field, Ji east offshore oilfield, Shengli Oil Field, Xinjiang Oilfield, Daqing oil field
Deng.The Sudan in 1996 and black square woods lattice-the Sudan's pipeline of Chinese collaborative building can transport crude oil at normal temperatures and pressures, because
The pour point depressant for crude oil that joined low dosage makes the condensation point of crude oil reduce 9 DEG C or so.Even to this day, the country is also in a plurality of crude oil pipe
Pour point depressant for crude oil has been used in line, and achieves certain function and effect.
80% or more the crude oil of each elephant output in China is all waxy crude oil, and wax content is mostly 15%~37%.Contain
Wax crude oil is constantly precipitated, when wax partial crystallization goes out in surface duct transportational process as the wax in the continuous reduction crude oil of temperature is brilliant
Amount may block oil pipeline when reaching a certain level.Since the brilliant a large amount of precipitations of wax cause serious shadow to the mobility of crude oil
It rings, so that exploitation and transportation cost greatly increase, so reducing the analysis of wax crystalline substance in transportational process by the condensation point for reducing crude oil
Out, improve crude oil fluidity, have great role in terms of save the cost and raising.It reduces both at home and abroad at present former
The common method of oil freezing point has physics pour point depression method and chemical pour-point depression method, and physical method reduces original mainly by way of heating
Oily condensation point, but this method usually requires very high temperature, and energy-output ratio is excessive, and cost is also higher.Chemical method be exactly to
Pour-point depressant is added in crude oil, the wax-crystal structure form of script in crude oil can be changed in pour-point depressant, so that it is not easy crystallization and is precipitated, with object
Pour point depression method is managed compared to chemical pour-point depression method is more convenient and economical and effective.
Summary of the invention
It is molten that the present invention for the disadvantages of existing pour-point depressant depression effeCt is bad at present provides a kind of quadripolymer oil
The preparation method of property pour point depressant for crude oil.The polymer molecular weight matches with the wax in crude oil, can be very good to inhibit wax crystalline substance
Growth aggregation, to reduce the condensation point of crude oil.The raw material sources of the pour-point depressant are extensive, and synthesis technology is simple, at low cost, seldom
Dosage under can significantly reduce condensation point of crude oil.
Polymer pour-point depressant synthetic route of the invention is carried out by the chemical reaction of following two step:
1. esterification:
2. polymerization reaction:
Beneficial effects of the present invention:
(1) present invention provides a kind of preparation method of quadripolymer oil soluble crude oil pour-point depressant, and this method raw material obtains
Relatively easily, production procedure is simple, and yield is high.
(2) wax in the polymer molecular weight and crude oil obtained by the present invention matches, and the dissolubility in crude oil is good, can
To inhibit the growth of wax crystalline substance to assemble well, to reduce the condensation point of crude oil.
(3) quadripolymer pour point depressant for crude oil provided by the invention is relatively small with dosage, depression effeCt is significantly special
Point.
Detailed description of the invention
Fig. 1 is the infrared spectrum of one products therefrom of embodiment
Fig. 2 is the infrared spectrum of two products therefrom of embodiment
Fig. 3 is the infrared spectrum of three products therefrom of embodiment
Fig. 4 is the infrared spectrum of example IV products therefrom
Fig. 5 is the relational graph of product of the present invention dosage and depression effeCt
Specific embodiment
Embodiment one:
A kind of preparation method of quadripolymer oil soluble crude oil pour-point depressant the following steps are included:
(1) synthesis of octadecyl methacrylate
The ratio that methacrylic acid and octadecyl alcolol are 1.2:1 in molar ratio is added equipped with thermometer, reflux condensing tube, is divided
In the three-necked flask of hydrophone and azeotropic agent and solvent toluene, magnetic agitation is warming up to 60 DEG C, and reactant is allowed sufficiently to dissolve, and adds
The catalyst p-methyl benzenesulfonic acid of 1.2wt% and the hydroquinone of polymerization retarder of 0.5wt% continue magnetic agitation and are warming up to specified temperature
Degree, after reacting a period of time, when water surface site no longer changes in water segregator, reaction terminates.In order to remove extra reactant
With solvent, needs that the crude product of acquisition is first carried out vacuum decompression distillation by Rotary Evaporators, be then 5% with mass fraction
NaOH solution is washed 4-5 times.A period of time will be stood with the water washed crude product of buck, measure the PH of upper solution to alkalescent
Afterwards, it is repeatedly washed with distilled water to neutrality, is finally dried in vacuo products therefrom, obtain octadecyl methacrylate.
(2) synthesis of polymer
Octadecyl methacrylate, maleic anhydride, styrene, acrylamide are added by the molar ratio of 3:1:2:0.5
Entering in the four-hole boiling flask equipped with thermometer, condenser pipe, agitating device, nitrogen conduit and solvent toluene, stirring is warming up to 50 DEG C, to
After reactant is completely dissolved, leads to nitrogen 20min, eliminate the air in flask, continues stirring and be warming up to reaction temperature, in nitrogen atmosphere
Lower isothermal reaction specified time is enclosed, during the reaction by the toluene solution dropping liquid of the benzoyl peroxide of 1.0wt% (BPO)
Funnel is added in flask in four times in 2h.After reaction, crude product is subjected to vacuum decompression distillation with Rotary Evaporators,
Gained liquid is washed repeatedly with excessive dehydrated alcohol again, unreacted monomer and excessive solvent are eliminated, finally by products therefrom
It is dried to obtain quaternary oil-soluble pour-point depressant.
Embodiment two:
A kind of preparation method of quadripolymer oil soluble crude oil pour-point depressant the following steps are included:
(1) synthesis of octadecyl methacrylate
Specific preparation method is identical as step (1) in embodiment one.
(2) synthesis of polymer
Octadecyl methacrylate, maleic anhydride, styrene, acrylamide are added by the molar ratio of 3:1:2:1
In four-hole boiling flask equipped with thermometer, condenser pipe, agitating device, nitrogen conduit and solvent toluene, stirring is warming up to 50 DEG C, to anti-
After answering object to be completely dissolved, lead to nitrogen 20min, eliminate the air in flask, continues stirring and be warming up to reaction temperature, in nitrogen atmosphere
Lower isothermal reaction specified time will during the reaction leak the toluene solution of the benzoyl peroxide of 1.0wt% (BPO) with dropping liquid
Bucket is added in flask in four times in 2h.After reaction, crude product is subjected to vacuum decompression distillation with Rotary Evaporators, then
Gained liquid is washed repeatedly with excessive dehydrated alcohol, unreacted monomer and excessive solvent is eliminated, finally does products therefrom
It is dry to obtain quaternary oil-soluble pour-point depressant.
Embodiment three:
A kind of preparation method of quadripolymer oil soluble crude oil pour-point depressant the following steps are included:
(1) synthesis of octadecyl methacrylate
Specific preparation method is identical as step (1) in embodiment one.
(2) synthesis of polymer
Octadecyl methacrylate, maleic anhydride, styrene, acrylamide are added by the molar ratio of 5:1:2:0.5
Entering in the four-hole boiling flask equipped with thermometer, condenser pipe, agitating device, nitrogen conduit and solvent toluene, stirring is warming up to 50 DEG C, to
After reactant is completely dissolved, leads to nitrogen 20min, eliminate the air in flask, continues stirring and be warming up to reaction temperature, in nitrogen atmosphere
Lower isothermal reaction specified time is enclosed, during the reaction by the toluene solution dropping liquid of the benzoyl peroxide of 1.0wt% (BPO)
Funnel is added in flask in four times in 2h.After reaction, crude product is subjected to vacuum decompression distillation with Rotary Evaporators,
Gained liquid is washed repeatedly with excessive dehydrated alcohol again, unreacted monomer and excessive solvent are eliminated, finally by products therefrom
It is dried to obtain quaternary oil-soluble pour-point depressant.
Example IV:
A kind of preparation method of quadripolymer oil soluble crude oil pour-point depressant the following steps are included:
(1) synthesis of octadecyl methacrylate
Specific preparation method is identical as step (1) in embodiment one.
(2) synthesis of polymer
Octadecyl methacrylate, maleic anhydride, styrene, acrylamide are added by the molar ratio of 5:1:2:1
In four-hole boiling flask equipped with thermometer, condenser pipe, agitating device, nitrogen conduit and solvent toluene, stirring is warming up to 50 DEG C, to anti-
After answering object to be completely dissolved, lead to nitrogen 20min, eliminate the air in flask, continues stirring and be warming up to reaction temperature, in nitrogen atmosphere
Lower isothermal reaction specified time will during the reaction leak the toluene solution of the benzoyl peroxide of 1.0wt% (BPO) with dropping liquid
Bucket is added in flask in four times in 2h.After reaction, crude product is subjected to vacuum decompression distillation with Rotary Evaporators, then
Gained liquid is washed repeatedly with excessive dehydrated alcohol, unreacted monomer and excessive solvent is eliminated, finally does products therefrom
It is dry to obtain quaternary oil-soluble pour-point depressant.
Embodiment five:
Crude oil sample is Tarim Oilfield dewatered oil, TulufanHami oil field block dewatered oil.Condensation point of crude oil measurement uses
Examples 1 to 4 products obtained therefrom is pressed 0.5% quality by the method provided in GB/T 510-83 " petroleum products questionable points measuring method "
Than being added in two kinds of crude oil, depression effeCt is measured after keeping the temperature 30min at 60 DEG C.The variation of condensation point with pour point depression degree (△ SP) come
It indicates.Examples 1 to 4 resulting product has certain depression effeCt to two kinds of products, dosage under the same conditions, implement
Four products obtained therefrom depression effeCt of example is better than other three kinds of products.Test result is shown in Tables 1 and 2.
Embodiment six:
Using the sample of example IV preparation as research object, the relationship of product additive amount and depression effeCt is investigated, is as a result seen
Fig. 5.The product is to the depression effeCt of two kinds of crude oil as the increase of dosage all shows becoming for first increases and then decreases as shown in Figure 5
Gesture, when dosage is 0.5wt%, pour point depression rate reaches maximum, so selected 0.5wt% is optimal dosage.
Depression effeCt of 1 pour-point depressant of table to Oil In Tarim Basin
2 pour-point depressant of table breathes out the depression effeCt of crude oil to spitting
Claims (5)
1. a kind of quadripolymer oil soluble crude oil pour-point depressant and preparation method, which is characterized in that the preparation method includes following
Step:
(1) using methacrylic acid and octadecyl alcolol as raw material, the two molar ratio is 1.2:1, q. s. toluene as azeotropic agent and solvent,
P-methyl benzenesulfonic acid is catalyst, and hydroquinone is polymerization inhibitor, octadecyl methacrylate is made by esterification, by acquisition
Crude product carries out vacuum decompression distillation by Rotary Evaporators, is then washed 4-5 times with the NaOH solution that mass fraction is 5%,
A period of time will be stood with the water washed crude product of buck, after the PH to alkalescent for measuring upper solution, is repeatedly washed with distilled water
It washs to neutrality, is finally dried in vacuo products therefrom, obtain intermediate product；
(2) under nitrogen protection, octadecyl methacrylate, maleic anhydride, acrylamide and styrene are added and solvent is housed
In the four-hole boiling flask of toluene, dissolution is sufficiently stirred in heating, is warming up to 90 DEG C, is added catalyst benzoyl peroxide (BPO), permanent
Crude product is carried out vacuum decompression distillation with Rotary Evaporators, then gained liquid is washed with excessive dehydrated alcohol by temperature polymerization 8h
Repeatedly, unreacted monomer and excessive solvent are eliminated, products therefrom is finally dried to obtain quaternary oil-soluble pour-point depressant.
2. (1) is described according to claim 1, a kind of quadripolymer oil soluble crude oil pour-point depressant and preparation method, feature
It is, the amount of catalyst p-methyl benzenesulfonic acid accounts for the 1.2% of reactant gross mass.
3. (1) is described according to claim 1, a kind of quadripolymer oil soluble crude oil pour-point depressant and preparation method, feature
It is, the amount of hydroquinone of polymerization retarder accounts for the 0.5% of reactant gross mass.
4. (2) are described according to claim 1, a kind of quadripolymer oil soluble crude oil pour-point depressant and preparation method, feature
It is, polymerization reaction carries out under nitrogen protection.
5. (2) are described according to claim 1, a kind of quadripolymer oil soluble crude oil pour-point depressant and preparation method, feature
It is, use benzoyl peroxide (BPO) as catalyst, the amount of benzoyl peroxide (BPO) accounts for reactant gross mass
1.0%.
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| CN201910799582.7A CN110437371A (en) | 2019-08-28 | 2019-08-28 | A kind of quadripolymer oil soluble crude oil pour-point depressant and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922955A (en) * | 2019-12-16 | 2020-03-27 | 西南石油大学 | Nano composite material high-wax thick oil pour point depression and viscosity reduction agent and preparation method thereof |
| CN114634599A (en) * | 2020-12-16 | 2022-06-17 | 中国石油化工股份有限公司 | Pour point depressant with low-temperature fluidity and preparation method and application thereof |
| WO2022262213A1 (en) * | 2021-06-16 | 2022-12-22 | 德仕能源科技集团股份有限公司 | Method for preparing fumaric acid pour point depressant for crude oil |
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| CN1564831A (en) * | 2001-08-08 | 2005-01-12 | 策卡有限公司 | Acrylic polymer latex dispersions as additives for inhibiting paraffin deposits in crude oils and compositions containing same |
| CN103184043A (en) * | 2013-02-28 | 2013-07-03 | 大连大学 | Crude oil pour point depressant and preparation method thereof |
| CN104530306A (en) * | 2014-12-11 | 2015-04-22 | 青岛佰众化工技术有限公司 | Synthesis method of polymethacrylate pour point depressant |
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2019
- 2019-08-28 CN CN201910799582.7A patent/CN110437371A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1564831A (en) * | 2001-08-08 | 2005-01-12 | 策卡有限公司 | Acrylic polymer latex dispersions as additives for inhibiting paraffin deposits in crude oils and compositions containing same |
| CN103184043A (en) * | 2013-02-28 | 2013-07-03 | 大连大学 | Crude oil pour point depressant and preparation method thereof |
| CN104530306A (en) * | 2014-12-11 | 2015-04-22 | 青岛佰众化工技术有限公司 | Synthesis method of polymethacrylate pour point depressant |
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| JINGCHANG WANG 等: "Research on Performance of the monomers about Acrylic pour point depressant", 《ADVANCED MATERIALS RESEARCH》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922955A (en) * | 2019-12-16 | 2020-03-27 | 西南石油大学 | Nano composite material high-wax thick oil pour point depression and viscosity reduction agent and preparation method thereof |
| CN110922955B (en) * | 2019-12-16 | 2022-06-03 | 西南石油大学 | Nano composite material high-wax thick oil pour point depression and viscosity reduction agent and preparation method thereof |
| CN114634599A (en) * | 2020-12-16 | 2022-06-17 | 中国石油化工股份有限公司 | Pour point depressant with low-temperature fluidity and preparation method and application thereof |
| CN114634599B (en) * | 2020-12-16 | 2023-12-01 | 中国石油化工股份有限公司 | Pour point depressant with low-temperature fluidity and preparation method and application thereof |
| WO2022262213A1 (en) * | 2021-06-16 | 2022-12-22 | 德仕能源科技集团股份有限公司 | Method for preparing fumaric acid pour point depressant for crude oil |
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Application publication date: 20191112 |