CN110283580B - Pour point depressing and paraffin inhibitor and its prepn - Google Patents
Pour point depressing and paraffin inhibitor and its prepn Download PDFInfo
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Abstract
The invention discloses a pour point depressing and paraffin preventing agent, wherein the pour point depressing and paraffin preventing agent comprises: a porous polymer, and the porous polymer may co-crystallize and/or adsorb with wax in the crude oil. Wherein the surface and the interior of the porous polymer comprise alkyl side chains, and the alkyl side chains can be eutectic and/or adsorbed with wax in crude oil. By the mode, the low-temperature rheological property of the wax-containing crude oil is effectively improved, and the wax deposition on the pipe wall is reduced.
Description
Technical Field
The invention relates to the technical field of pour point depressing and wax preventing of crude oil, in particular to a pour point depressing and wax preventing agent and a preparation method thereof.
Background
Waxy crude oil is an important fossil energy source and is widely distributed around the world. The wax in the waxy crude oil is mainly C16-C40 normal paraffin, and meanwhile, most waxy crude oil also comprises a certain amount of non-hydrocarbon colloid and asphaltene, so the waxy crude oil has high condensation point, poor fluidity at normal temperature and complex rheological behavior, and the separated wax is easy to deposit on the pipe wall, thereby causing the pipeline transportation difficulty of the oil.
In the prior art, the pour point depressing and wax preventing agent cannot effectively improve the low-temperature rheological property of the wax-containing crude oil, reduce the deposition of wax on the pipe wall and improve the economical efficiency and safety of oil transportation.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a pour point depressing and paraffin preventing agent and a preparation method thereof, and aims to solve the problems that the pour point depressing and paraffin preventing agent cannot effectively improve the low-temperature rheological property of wax-containing crude oil and reduce the deposition of wax on the pipe wall in the prior art.
The technical scheme of the invention is as follows:
a pour point depressing and wax inhibiting agent, wherein the pour point depressing and wax inhibiting agent comprises:
a porous polymer, and the porous polymer may co-crystallize and/or adsorb with wax in the crude oil.
Wherein the surface and the interior of the porous polymer comprise alkyl side chains, and the alkyl side chains can be eutectic and/or adsorbed with wax in crude oil.
Wherein the monomer of the porous polymer comprises acrylic acid high carbon alcohol ester, and the carbon number of a long chain group in the acrylic acid high carbon alcohol ester is not less than 16.
Wherein the internal pore structure of the porous polymer comprises cells and pores;
when the porous polymer is prepared by adopting a high internal phase emulsion template method, the pores are generated by internal phase dispersed liquid drops, and the pores are generated by a pore-foaming agent.
Wherein the diameter of the cells is 0.5-600 μm, and the diameter of the pores is 0.1-300 μm.
Wherein the particle size range of the porous polymer is 100nm to 10 μm.
Wherein the addition amount of the porous polymer in the crude oil is 10-500 mg/Kg.
A method for preparing a pour point depressing and wax preventing agent, wherein the method comprises the following steps:
providing a monomer, a cross-linking agent and an emulsifier of a porous polymer, and melting at a certain temperature to obtain a first mixture;
emulsifying the first mixture with a certain amount of water under stirring for a period of time to obtain a water-in-oil type high internal phase emulsion;
standing and reacting the water-in-oil type high internal phase emulsion and an initiator for a period of time under the nitrogen atmosphere to obtain the pour point depressing and paraffin preventing agent;
wherein the monomer of the porous polymer comprises acrylic acid high carbon alcohol ester, and the carbon number of a long chain group in the acrylic acid high carbon alcohol ester is not less than 16.
Wherein, in the process of preparing the first mixture, the method further comprises the following steps:
adding a silane coupling agent.
Wherein the method for obtaining the pour point depressing and wax preventing agent by standing and reacting the water-in-oil type high internal phase emulsion and the initiator for a period of time under the nitrogen atmosphere comprises the following steps:
standing and reacting the water-in-oil type high internal phase emulsion and an initiator for a period of time under the nitrogen atmosphere to obtain the porous polymer;
grinding the porous polymer to a particle size range of 100nm to 10 μm.
Has the advantages that: different from the prior art, the pour point depressing and wax preventing agent comprises a porous polymer, and the porous polymer can be subjected to eutectic crystallization and/or adsorption with wax in crude oil in the cooling process, and wax molecules can be crystallized and separated out in through holes, so that the wax in the crude oil and the pour point depressing and wax preventing agent are combined more tightly, the porous polymer is used as a crystallization template of the wax molecules, a wax crystal aggregate with a more regular and compact structure is formed, the flowing property of the crude oil is greatly improved, and the pour point of the crude oil is reduced; and the polar group in the porous polymer increases the interfacial tension between the wax and the oil phase, and the wax is difficult to crystallize and separate out by improving the nucleation barrier of the wax, so that the deposition of the wax on the pipe wall is reduced.
Drawings
FIG. 1 is a scanning electron micrograph of an embodiment of the porous polymer of the present invention.
FIG. 2 is a schematic flow chart of an embodiment of the method for preparing the pour point depressing and paraffin preventing agent.
Fig. 3 is a flowchart illustrating an embodiment of S300 in fig. 2.
Detailed Description
The invention provides a pour point depressing and paraffin control agent and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Before describing the technical scheme of the application, the characteristics of the wax in the crude oil are introduced.
The wax in the wax-containing crude oil mainly refers to C16-C40 normal paraffin, and most wax-containing crude oil also contains a certain amount of non-hydrocarbon colloid and asphaltene components. The asphaltene is a condensed aromatic ring system non-hydrocarbon substance with the largest molecular weight and the strongest polarity in the crude oil; asphaltene molecules are insoluble in crude oil and are often dispersed in the crude oil in the form of associated colloidal particles, and the colloids adsorbed on the surface of the associated colloidal particles act as asphaltene stabilizers. The wax content of the wax-containing crude oil is high, and wax molecules begin to crystallize and separate out due to supersaturation at higher oil temperature. Many studies prove that the associated asphaltene colloidal particles are natural wax crystal modifiers in crude oil, can participate in wax precipitation process through the action of heterogeneous nucleation points, further initiate to form a large amount of small wax crystals (submicron to several microns) in the wax-containing crude oil, and generate a larger crystal/liquid interface. On one hand, the liquid oil bound in the solvent layer on the surface of the wax crystal particles is increased due to the larger crystal/liquid interface; on the other hand, the larger crystal/liquid interface also promotes the interaction between wax crystal particles. Due to the factors, at a relatively low wax precipitation amount (about 2 wt%) and a relatively high temperature, the wax-containing crude oil can be gelled due to the formation of a loose wax crystal three-dimensional network structure, and shows complex non-Newtonian fluid characteristics of viscoelasticity, thixotropy, yield and the like. Therefore, the wax-containing crude oil has high condensation point, poor fluidity at normal temperature and complex rheological behavior, and precipitated wax crystals are easy to deposit on the pipe wall, which causes difficulty in pipeline transportation of such oil products.
The application discloses a pour point depressing and wax preventing agent, wherein the pour point depressing and wax preventing agent comprises a porous polymer, and the porous polymer can be eutectic and/or adsorbed with wax in crude oil. Specifically, the porous polymer can be eutectic and/or adsorbed with wax molecules in the crude oil during the temperature reduction process. Wherein the wax molecules mainly comprise normal alkanes of C16-C40.
In the embodiment, the porous polymer can be subjected to eutectic crystallization and/or adsorption with wax in the crude oil in the cooling process, and wax molecules can be crystallized and separated out in the through holes, so that the wax in the crude oil and the pour point depressing and wax preventing agent are more tightly combined, the porous polymer is used as a crystallization template of the wax molecules to form wax crystal aggregates with more regular and compact structures, the flowing property of the crude oil is greatly improved, and the condensation point of the crude oil is reduced; and the polar group in the porous polymer increases the interfacial tension between the wax and the oil phase, and the wax is difficult to crystallize and separate out by improving the nucleation barrier of the wax, so that the deposition of the wax on the pipe wall is reduced.
Furthermore, the surface and the interior of the porous polymer comprise alkyl side chains, and the alkyl side chains can be eutectic and/or adsorbed with the wax in the crude oil, so that the wax in the crude oil and the surface and the interior of the porous polymer comprise the alkyl side chains through eutectic to form a stable crystal structure, and the wax precipitation caused by separation of the wax in the crude oil from the porous polymer can be effectively avoided even under the condition of changing external environment.
Further, the monomer of the porous polymer comprises acrylic acid high carbon alcohol ester, and the carbon number of a long chain alkyl side chain in the acrylic acid high carbon alcohol ester is not less than 16, for example, the carbon number of the long chain alkyl side chain is 16, 18 or 20, and the like, because when the carbon number of the long chain alkyl side chain is less than 16, the interaction force between the carbon number of the long chain alkyl side chain and a wax molecule is insufficient, and eutectic precipitation with the wax molecule is difficult. Therefore, the carbon number of the long chain alkyl side chain is not particularly limited herein, as long as the carbon number of the long chain alkyl side chain in the higher alcohol acrylate can be eutectic and/or adsorbed with the wax in the crude oil.
In another embodiment, referring to fig. 1, fig. 1 is a scanning electron micrograph of an embodiment of a porous polymer according to the present invention, the internal pore structure of the porous polymer comprising cells and pores; when the porous polymer is prepared using a high internal phase emulsion templating method, the pores are created from internal phase dispersed droplets, the pores being created from a porogen. Specifically, the pores can effectively adsorb crude oil, the pores can provide better fluid flowing places, when the pour point depressing and wax preventing agent disclosed by the application is added into the crude oil, the crude oil is combined with the porous polymer through the pores and flows in the porous polymer through the pores, and during the contact process of the crude oil and the porous polymer, the wax in the crude oil is eutectic and/or adsorbed with alkyl side chains on the surface or in the porous polymer, so that the wax in the crude oil is more tightly combined with the pour point depressing and wax preventing agent, and the solubility of the wax in the crude oil is increased, and then the precipitation of the wax is reduced; and the polar group in the porous polymer increases the interfacial tension between the wax and the oil phase, and the wax is difficult to crystallize and separate out by improving the nucleation barrier of the wax, so that the deposition of the wax on the pipe wall is reduced, and the low-temperature rheological property of the wax-containing crude oil is further improved.
Wherein the high internal phase emulsion is an emulsion having a dispersed phase volume of 74% or more; the high internal phase emulsion template method is a method of taking a polyhedral emulsion droplet as a template, carrying out polymerization reaction on the surface of the droplet at a certain temperature, and washing and drying after the polymerization is finished to obtain the porous polymer material. In this embodiment, the inner dispersed phase comprises water; the pore-forming agent includes one or more of toluene, cyclohexane or chlorobenzene, and specifically, which dispersion phase is selected and which pore-forming agent is determined according to the preparation environment and the product requirements, so that the method is not limited.
Further, the diameter of the cells is 0.5 to 600. mu.m, e.g., 0.5. mu.m, 10 μm, 100. mu.m, 300. mu.m, 600 μm, etc., and the pore size of the cells is not more specifically defined herein, so long as it promotes the flow of crude oil therein; the pores have a diameter of 0.1-300 μm, such as, 0.1 μm, 10 μm, 100 μm, 200 μm, 300 μm, or the like, and in one embodiment, the pores have a diameter of 1-20%, such as, 1%, 5%, 10%, or 20%, or the like, of the pore size of the pores, which is not more specifically limited herein, so long as effective adsorption of crude oil is possible.
Furthermore, the conventional polymer pour point depressant is in a chain or comb shape, and the structure of the conventional polymer pour point depressant is damaged to a certain extent by pipe flow shearing and high-speed shearing of a pump in long-distance pipeline transportation, and the interaction between the conventional polymer pour point depressant and wax is also influenced, so that the conventional polymer pour point depressant has poor timeliness, shear resistance, repeated heating resistance and the like. Compared with a chain or comb-shaped traditional pour point depressant, the porous polymer in the pour point depressant and paraffin inhibitor has a three-dimensional through hole structure, so that the structure of the pour point depressant and paraffin inhibitor is more stable; in addition, the pores and pores in the porous polymer enable the porous polymer to present a highly-penetrated pore-channel structure, can play a role of a wax crystallization template in the wax-containing crude oil, promotes the formation of wax crystals with larger size and more compact structure, and thus stronger interaction exists between the porous polymer and the wax. It is clear that the porous polymer has more advantages in terms of microstructure and interaction with wax in crude oil, and therefore exhibits better aging, shear resistance against repeated heating, and a stronger pour point depressing and viscosity reducing effect.
Further, in order to ensure that the porous polymer is sufficiently contacted with crude oil for effective adsorption, the specific surface area of the porous polymer should be large enough, that is, the particle size of the porous polymer should not be too large; in order to ensure that the crude oil flows and diffuses in the three-dimensional pore structure of the porous polymer sufficiently and is subjected to eutectic crystallization and/or adsorption with the porous polymer, the particle size of the porous polymer is not small enough. In the present embodiment, the particle size of the porous polymer in the anti-condensation and anti-wax agent is in the range of 100nm to 10 μm, such as 100nm,500nm,1 μm or 10 μm, which is not only convenient for molding, but also beneficial for obtaining good anti-condensation and anti-pour effects. Of course, the particle size of the porous polymer can be selected according to actual conditions for different crude oils and different requirements for wax inhibition and pour point depression, and is not particularly limited.
In another embodiment, the amount of the porous polymer added to the crude oil is 10 to 500mg/Kg, such as 10mg/Kg, 50mg/Kg, 100mg/Kg, 200mg/Kg or 200mg/Kg, and the like, and specifically, the amount of the porous polymer added is related to the structure of the porous polymer and the properties of the crude oil, and can be determined according to practical situations to obtain better wax-inhibition pour-point depressing effect, and is not limited herein.
In order to solve the technical problem, the application also discloses a preparation method of the pour point depressing and paraffin preventing agent. Referring to fig. 2, fig. 2 is a schematic flow chart of an embodiment of a method for preparing the pour point depressing and wax preventing agent of the present application, wherein the method comprises:
step S100, providing a monomer, a cross-linking agent and an emulsifying agent of the porous polymer, and melting at a certain temperature to obtain a first mixture.
In the step S100, the monomer of the porous polymer includes a high carbon alcohol acrylate, the number of carbons of the long chain group in the high carbon alcohol acrylate is not less than 16, for example, the number of carbons of the long chain group is 16, 18 or 20, etc., in any case, as long as the long chain group in the high carbon alcohol acrylate can be eutectic and/or adsorbed with the wax in the crude oil; the crosslinking agent comprises divinylbenzene; the emulsifier comprises span series surfactant, such as span-80, etc. Further, the amount of the cross-linking agent is 1-10% of the mass of the monomer, such as 1%, 5% or 10%; the amount of emulsifier is 25-35% of the mass of the monomers, e.g., 25%, 30%, or 35%.
And step S200, emulsifying the first mixture and a certain amount of water under the stirring action for a period of time to obtain the water-in-oil type high internal phase emulsion.
In step S200, water is added in an amount greater than 74% of the total volume of water and monomer, that is, the volume ratio of the water to the first mixture is greater than 74% in a period of time in which the first mixture is emulsified with a certain amount of water under stirring; further, the stirring method may be mechanical stirring or magnetic stirring, and in one embodiment, the emulsifying is performed for 30 to 60 minutes, such as 30 minutes, 45 minutes, or 60 minutes, under magnetic stirring.
And step S300, standing and reacting the water-in-oil type high internal phase emulsion and an initiator for a period of time in a nitrogen atmosphere to obtain the pour point depressing and wax preventing agent.
Further, the process of preparing the first mixture further comprises: adding a silane coupling agent when preparing the emulsion, wherein the adding amount is 100-1000 ppm. In the embodiment, the silane coupling agent is added, so that the stability of the porous polymer structure is improved, and the using effect of the pour point depressing and wax preventing agent is improved.
Further, referring to fig. 3, fig. 3 is a schematic flow chart of an embodiment of S300 in fig. 2, wherein the method for obtaining the pour point depressing and wax preventing agent by allowing the water-in-oil high internal phase emulsion and the initiator to stand and react for a period of time under a nitrogen atmosphere comprises:
and S310, standing and reacting the water-in-oil type high internal phase emulsion and an initiator for a period of time in a nitrogen atmosphere to obtain the porous polymer. Specifically, the water-in-oil type high internal phase emulsion is transferred into a mold by pouring and the like, and is subjected to standing reaction with an initiator under a nitrogen atmosphere for a period of time to obtain the porous polymer. In this embodiment, the amount of the initiator is 0.5 to 1.5% by mass of the monomer, e.g., 0.5%, 1%, 1.5%, etc.; further, the initiator comprises azobisisobutyronitrile.
Step S320, grinding the porous polymer to a particle size range of 100 nm-10 μm.
In step S320, in order to ensure that the porous polymer is sufficiently contacted with the crude oil for effective adsorption, the specific surface area of the porous polymer should be large enough, that is, the particle size of the porous polymer should not be too large; in order to ensure that the crude oil flows and diffuses in the three-dimensional pore structure of the porous polymer sufficiently and is subjected to eutectic crystallization and/or adsorption with the porous polymer, the particle size of the porous polymer is not small enough. In the embodiment, the particle size range of the porous polymer in the pour point depressing and wax preventing agent is 100nm to 10 μm, such as 100nm,500nm,1 μm or 10 μm, and the like, so that the pour point depressing and wax preventing agent is not only convenient to form, but also beneficial to obtaining a good wax depressing and pour point preventing effect. Of course, the particle size of the porous polymer can be selected according to actual conditions for different crude oils and different requirements for wax inhibition and pour point depression, and is not particularly limited.
The technical solution of the present application is further illustrated by the following examples:
example 1:
heating and melting 26mL of octadecyl acrylate (reaction monomer), divinylbenzene (crosslinking agent) accounting for 10% of the weight of the octadecyl acrylate, and span-80 (emulsifying agent) accounting for 30% of the weight of the octadecyl acrylate at 70 ℃ to obtain a first mixture;
emulsifying the first mixture with 74mL of distilled water under stirring for 30min to prepare a water-in-oil high internal phase emulsion;
taking azodiisobutyronitrile accounting for 1% of the octadecyl acrylate as an initiator, transferring the prepared water-in-oil type high internal phase emulsion into a mold, and standing and reacting for 1 day under the protection of nitrogen atmosphere to obtain the porous polymer; grinding the porous polymer to a particle size range of 100 nm-10 mu m to obtain the pour point depressing and paraffin preventing agent 1.
Example 2:
heating and melting 24mL of cetyl acrylate (reaction monomer), divinylbenzene (crosslinking agent) accounting for 5% of the mass of the cetyl acrylate, and span-80 (emulsifying agent) accounting for 30% of the mass of the cetyl acrylate at 60 ℃ to obtain a first mixture;
emulsifying the first mixture with 76mL of distilled water under stirring for 30min to prepare a water-in-oil high internal phase emulsion;
taking azodiisobutyronitrile with the mass of 1% of the hexadecyl acrylate as an initiator, transferring the prepared water-in-oil type high internal phase emulsion into a mold, and standing and reacting for 1 day under the protection of nitrogen atmosphere to obtain the porous polymer; and grinding the porous polymer to a particle size range of 100 nm-10 mu m to obtain the pour point depressing and paraffin preventing agent 2.
Example 3:
heating and melting 22mL of eicosyl acrylate (reaction monomer), divinylbenzene (crosslinking agent) accounting for 10% of the mass of the eicosyl acrylate, and span-80 (emulsifier) accounting for 30% of the mass of the docosyl acrylate at 80 ℃ to obtain a first mixture;
emulsifying the first mixture with 78mL of distilled water under stirring for 30min to prepare a water-in-oil high internal phase emulsion;
taking azodiisobutyronitrile accounting for 1% of the weight of the eicosyl acrylate as an initiator, transferring the prepared water-in-oil type high internal phase emulsion into a mold, and standing and reacting for 1 day under the protection of nitrogen atmosphere to obtain the porous polymer; and grinding the porous polymer to a particle size range of 100 nm-10 mu m to obtain the pour point depressing and paraffin preventing agent 3.
The pour point depressing and paraffin preventing agent 1 is taken as an example to test the effect of the pour point depressing and paraffin preventing agent:
TABLE 1 pour point depressing and wax preventing Effect of pour point depressing and wax preventing agent 1 in different crude oils
As can be seen from Table 1, the addition of the pour point depressing and wax preventing agent 1 can effectively reduce the pour point, viscosity and accumulated wax precipitation amount of the crude oil.
Grinding the anti-condensation and anti-wax agent 1 until the particle size distribution is 100 nm-10 mu m, adding the anti-condensation and anti-wax agent into Changqing crude oil at the concentration of 10-500mg/kg, and comparing the condensation point, the apparent viscosity at 10 ℃ and the accumulated wax precipitation amount at 0 ℃ of the crude oil after adding different amounts of the anti-condensation and anti-wax agent into the following table 2.
TABLE 2 DENSATION WAX-PROOF AGENT FROM AND FROM CRYSTALLINE OIL ADDITION, AN apparent VISCOSITY AT 10 ℃ AND A cumulative WAX-SEPARATION METER AT 0 ℃ in Changqing CRUDE OIL
As can be seen from Table 2, the anti-condensation and anti-wax agent can obviously reduce the condensation point, the low-temperature viscosity and the wax deposition amount of crude oil, and has obvious repeated heating resistance, mechanical shearing resistance and other capabilities; meanwhile, with the increase of the addition amount of the anti-condensation wax-proofing agent, the condensation point of the crude oil, the apparent viscosity at 10 ℃ and the accumulated wax precipitation amount at 0 ℃ are all obviously reduced, so that the anti-condensation wax-proofing agent can reduce the deposition of wax on the pipe wall, and further improve the low-temperature rheological property of the wax-containing crude oil.
In summary, the pour point depressing and paraffin inhibiting agent comprises a porous polymer, and the porous polymer can be subjected to eutectic crystallization and/or adsorption with wax in crude oil in the process of temperature reduction, and wax molecules can be crystallized and separated out in through holes, so that the wax in the crude oil and the pour point depressing and paraffin inhibiting agent are combined more tightly, the porous polymer is used as a crystallization template of the wax molecules, a wax crystal aggregate with a more regular and compact structure is formed, the flowing property of the crude oil is greatly improved, and the pour point of the crude oil is reduced; and the polar group in the porous polymer increases the interfacial tension between the wax and the oil phase, and the wax is difficult to crystallize and separate out by improving the nucleation barrier of the wax, so that the deposition of the wax on the pipe wall is reduced.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of the pour point depressing and wax preventing agent is characterized by comprising the following steps:
providing a monomer, a cross-linking agent and an emulsifier of a porous polymer, and melting at a certain temperature to obtain a first mixture;
emulsifying the first mixture with a certain amount of water under stirring for a period of time to obtain a water-in-oil type high internal phase emulsion;
standing and reacting the water-in-oil type high internal phase emulsion and an initiator for a period of time under the nitrogen atmosphere to obtain the pour point depressing and paraffin preventing agent;
wherein the monomer of the porous polymer comprises acrylic acid high carbon alcohol ester, and the carbon number of a long chain group in the acrylic acid high carbon alcohol ester is not less than 16;
the cross-linking agent comprises divinylbenzene in an amount of 1 to 10% by mass of the polymer monomers; the emulsifier comprises span emulsifier, and the dosage of the emulsifier is 25-35% of the mass of the monomer; the adding amount of the water is more than 74 percent of the total volume of the water and the monomer;
the process for preparing the first mixture further comprises: adding a silane coupling agent; the amount of the silane coupling agent added is 100-1000 ppm.
2. The method according to claim 1, wherein the water-in-oil type high internal phase emulsion and the initiator are allowed to stand and react for a period of time under a nitrogen atmosphere to obtain the pour point depressing and wax preventing agent comprises:
standing and reacting the water-in-oil type high internal phase emulsion and an initiator for a period of time under the nitrogen atmosphere to obtain the porous polymer;
grinding the porous polymer to a particle size range of 100nm to 10 μm.
3. A pour point depressing and wax inhibiting agent prepared by the method of any one of claims 1-2, the pour point depressing and wax inhibiting agent comprising:
a porous polymer, and the porous polymer can be eutectic and/or adsorbed with wax in crude oil;
the internal pore structure of the porous polymer comprises cells and pores;
when the porous polymer is prepared by adopting a high internal phase emulsion template method, the pores are generated by internal phase dispersed liquid drops, and the pores are generated by a pore-foaming agent.
4. The pour point depressing and wax inhibiting agent according to claim 3, wherein the surface and interior of the porous polymer comprises alkyl side chains that can co-crystallize and/or adsorb with wax in crude oil.
5. The pour point depressing and wax preventing agent according to claim 3, wherein the diameter of the cells is 0.5 to 600 μm and the diameter of the pores is 0.1 to 300 μm.
6. The pour point depressing and wax preventing agent as recited in claim 3, wherein the porous polymer is added in the crude oil in an amount of 10-500 mg/Kg.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1086964A2 (en) * | 1999-09-22 | 2001-03-28 | Ethyl Corporation | (Meth) acrylate copolymer pour point depressants |
| 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 |
| CN102127409A (en) * | 2011-01-10 | 2011-07-20 | 中国科学院化学研究所 | Crude oil viscosity-breaking pour-point depressant composition, and preparation method and application thereof |
| CN108997991A (en) * | 2018-07-17 | 2018-12-14 | 中国石油大学(华东) | A kind of compound pour-point depressant |
| CN109880016A (en) * | 2019-01-03 | 2019-06-14 | 华东理工大学 | The method for continuously preparing water-in-oil type High Internal Phase Emulsion and polymer porous material |
-
2019
- 2019-06-28 CN CN201910573534.6A patent/CN110283580B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1086964A2 (en) * | 1999-09-22 | 2001-03-28 | Ethyl Corporation | (Meth) acrylate copolymer pour point depressants |
| 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 |
| CN102127409A (en) * | 2011-01-10 | 2011-07-20 | 中国科学院化学研究所 | Crude oil viscosity-breaking pour-point depressant composition, and preparation method and application thereof |
| CN108997991A (en) * | 2018-07-17 | 2018-12-14 | 中国石油大学(华东) | A kind of compound pour-point depressant |
| CN109880016A (en) * | 2019-01-03 | 2019-06-14 | 华东理工大学 | The method for continuously preparing water-in-oil type High Internal Phase Emulsion and polymer porous material |
Non-Patent Citations (2)
| Title |
|---|
| 新型稠油油溶性降粘剂的合成与评价;张明阳;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20141015;第14页第2-3段、第19页第2.3节、第20-21页第2.4.1节第3段、第27页第3段 * |
| 稠油纳米降黏剂的合成与评价;汪健;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131115;第10页、第24页第3.2.2节、第26页第3.3.2节，第28页第3.3.3.1节 * |
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