CN108949221B - Magnetic dewaxing agent and magnetic dewaxing method - Google Patents
Magnetic dewaxing agent and magnetic dewaxing method Download PDFInfo
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- CN108949221B CN108949221B CN201810784505.XA CN201810784505A CN108949221B CN 108949221 B CN108949221 B CN 108949221B CN 201810784505 A CN201810784505 A CN 201810784505A CN 108949221 B CN108949221 B CN 108949221B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a magnetic dewaxing agent and a magnetic dewaxing method, wherein the magnetic dewaxing agent comprises magnetic nano particles and a polymer dewaxing agent coated on the peripheries of the magnetic nano particles(ii) a The magnetic nanoparticles comprise Fe3O4、γ‑Fe2O3、Co2O3One or a combination of two or more of NiO; the polymer dewaxing agent comprises a high-molecular polymer with nonpolar groups and polar groups in molecules, including homopolymers and copolymers; the molecular weight of the polymer dewaxing agent is 4000-100000; the non-polar group comprises a long chain alkyl group, and the polar group comprises an ester group, a ketone group, an amino group, an amide group and a sulfur group. Through the mode, the dewaxing process can be simplified, and the dewaxing cost can be reduced.
Description
Technical Field
The invention relates to the technical field of dewaxing, in particular to a magnetic dewaxing agent and a magnetic dewaxing method.
Background
Crude oil and product oil contain a certain amount of wax. These waxes consist of n-alkanes above C16. With the reduction of the temperature, the wax crystals are separated out and randomly lapped and wound in the crude oil to form a continuous three-dimensional crystal network, so that the crude oil is converted from a sol system to a gel system to form a gel structure with certain strength, and great challenges are brought to the exploitation, transportation and use of the crude oil.
In the prior art, wax in crude oil is usually separated by adding a dewaxing agent into the crude oil and uniformly mixing, separating out the wax in the process of cooling, and separating the dewaxed crude oil from the separated wax and the residual dewaxing agent by methods such as centrifugation. This makes the dewaxing process more complicated and costly.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a magnetic dewaxing agent and a magnetic dewaxing method, which aim to solve the problems of complicated dewaxing process and high dewaxing cost in the prior art.
The technical scheme of the invention is as follows:
a magnetic dewaxing agent, wherein the magnetic dewaxing agent comprises:
the wax remover comprises magnetic nanoparticles and a polymer wax remover coated on the peripheries of the magnetic nanoparticles;
the magnetic nanoparticles comprise Fe3O4、γ-Fe2O3、Co2O3One or a combination of two or more of NiO;
the polymer dewaxing agent comprises a high-molecular polymer with nonpolar groups and polar groups in molecules, including homopolymers and copolymers; the molecular weight of the polymer dewaxing agent is 4000-100000; the non-polar group comprises a long chain alkyl group, and the polar group comprises an ester group, a ketone group, an amino group, an amide group and a sulfur group.
Wherein the particle size of the magnetic nanoparticles is 5-50 nm.
Wherein the magnetic nanoparticles and the polymer dewaxing agent are compounded together by means of solution blending or melt blending.
Wherein the polymer dewaxing agent comprises polyacrylic acid high-carbon alcohol ester and/or polyethylene-vinyl acetate.
A magnetic dewaxing method, wherein the method comprises:
providing a magnetic dewaxing agent with preset mass, wherein the magnetic dewaxing agent comprises magnetic nanoparticles and a polymer dewaxing agent coated on the peripheries of the magnetic nanoparticles; the magnetic nanoparticles comprise Fe3O4、γ-Fe2O3、Co2O3One or a combination of two or more of NiO; the polymer dewaxing agent comprises a high-molecular polymer with nonpolar groups and polar groups in molecules, including homopolymers and copolymers; the molecular weight of the polymer dewaxing agent is 4000-100000; the non-polar group comprises a long chain alkyl group, and the polar group comprises an ester group, a ketone group, an amino group, an amide group and a sulfur group;
mixing the magnetic dewaxing agent with the preset mass with the oil to be treated with the preset mass to obtain a mixture;
cooling the mixture to a preset temperature or below, so that wax molecules in the oil product to be treated are crystallized on the surface of the magnetic dewaxing agent, and obtaining the magnetic dewaxing agent containing precipitated wax;
and applying a magnetic field to the mixture to precipitate the magnetic dewaxing agent.
Wherein, when the oil product to be treated with the preset mass is 100g, the magnetic dewaxing agent with the preset mass is 5-20 mg.
Wherein the preset temperature is the wax precipitation point of the oil product to be treated.
Wherein, still include before cooling to preset temperature to the mixture:
heating the mixture to 50-80 ℃, and stirring for 0.2-1h by adopting a mechanical stirring mode.
Wherein, the application of the magnetic field to the mixture to precipitate the magnetic dewaxing agent further comprises:
the mixture is filtered and the magnetic dewaxing agent including precipitated wax is separated from the mixture.
Wherein the magnetic field is from a permanent magnet or an electromagnet.
Has the advantages that: the magnetic dewaxing agent comprises magnetic nano particles and a polymer dewaxing agent coated on the peripheries of the magnetic nano particles; the magnetic nanoparticles comprise Fe3O4、γ-Fe2O3、Co2O3And NiO, or a combination of two or more of them. The structure of the polymer dewaxing agent wrapped at the periphery of the nano magnetic core can enable the polymer dewaxing agent to be in better contact with crude oil, and the dewaxing effect is improved. The magnetic dewaxing agent can be separated by an external magnetic field, and the dewaxed crude oil can be separated from the precipitated wax and the residual dewaxing agent without separation operations such as centrifugation, so that the dewaxing process is simplified and the dewaxing cost is reduced.
Drawings
FIG. 1 is a schematic structural view of a preferred embodiment of a magnetic dewaxing agent according to the present invention;
FIG. 2 is a flow chart of a preferred embodiment of a magnetic dewaxing method of the present invention.
Detailed Description
The present invention provides a magnetic dewaxing agent and a magnetic dewaxing method, and the present invention is further described in detail below in order to make the objects, technical schemes, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a preferred embodiment of a magnetic dewaxing agent according to the present invention, where the magnetic dewaxing agent includes a magnetic nanoparticle 100 and a polymer dewaxing agent 200 coated on the periphery of the magnetic nanoparticle; the magnetic nanoparticles 100 comprise Fe3O4、γ-Fe2O3、Co2O3One or a combination of two or more of NiO; the polymer dewaxing agent 200 comprises a high molecular polymer with nonpolar groups and polar groups in the molecules, including homopolymers and copolymers; the molecular weight of the polymer dewaxing agent 200 is 4000-100000; the non-polar group comprises a long chain alkyl group, and the polar group comprises an ester group, a ketone group, an amino group, an amide group and a sulfur group.
In the embodiment, the polymer dewaxing agent is better contacted with crude oil by adopting the structure that the polymer dewaxing agent is wrapped on the periphery of the nano magnetic core, so that the dewaxing effect is improved. The magnetic dewaxing agent can be separated by an external magnetic field, and the dewaxed crude oil can be separated from the precipitated wax and the residual dewaxing agent without separation operations such as centrifugation, so that the dewaxing process is simplified and the dewaxing cost is reduced.
In one embodiment, the magnetic nanoparticles 100 are spherical magnetic nanoparticles. The magnetic nanoparticles 100 have a particle size of 5-50nm, e.g., 5nm, 10nm, 20nm, 30nm, 40nm, or 50nm, and the specific surface area of the magnetic nanoparticles 100 is larger as the particle size of the magnetic nanoparticles 100 decreases. In order to provide a larger accommodating space for the polymer dewaxing agent 200 and ensure that the polymer dewaxing agent 200 can be sufficiently stretched to perform a dewaxing effect, the particle size of the magnetic nanoparticles 100 is 30 nm.
In one embodiment, the magnetic nanoparticles 100 and the polymeric dewaxing agent 200 are compounded together by solution blending or melt blending. The polymer dewaxing agent 200 can be coated on the periphery of the magnetic nanoparticles 100 by adopting a solution blending or melt blending mode, so that the magnetic dewaxing agent is obtained. In order to reduce the use of solvent and the stronger interaction between the magnetic nanoparticles 100 and the polymer dewaxing agent 200, the magnetic nanoparticles 100 and the polymer dewaxing agent 200 are compounded together by means of melt blending.
In one embodiment, the polymeric dewaxing agent includes a polyacrylic acid higher alcohol ester and/or polyethylene-vinyl acetate. Polyacrylic acid high-carbon alcohol ester and/or polyethylene-vinyl acetate are/is adopted as a polymer dewaxing agent and can be closely matched with the magnetic nanoparticles, so that the polymer dewaxing agent in the magnetic dewaxing agent is prevented from being separated from the magnetic nanoparticles in the using process. In order to obtain better dewaxing effect, the polymer dewaxing agent is a mixture of polyacrylic acid high-carbon alcohol ester and polyethylene-vinyl acetate. Of course, depending on the characteristics of the crude oil to be dewaxed, different polymeric dewaxed agents or combinations of polymeric dewaxed agents may be selected.
In order to solve the technical problem, the invention also provides a magnetic dewaxing method.
Referring to fig. 2, fig. 2 is a schematic flow chart of a magnetic dewaxing method according to a preferred embodiment of the present invention, the method including the steps of:
and S100, providing a magnetic dewaxing agent with preset mass.
In the step S100, the magnetic dewaxing agent includes magnetic nanoparticles and a polymer dewaxing agent coated on peripheries of the magnetic nanoparticles; the magnetic nanoparticles comprise Fe3O4、γ-Fe2O3、Co2O3One or a combination of two or more of NiO; the polymer dewaxing agent comprises a high-molecular polymer with nonpolar groups and polar groups in molecules, including homopolymers and copolymers; the molecular weight of the polymer dewaxing agent is 4000-100000; the non-polar group comprises a long chain alkyl group, and the polar group comprises an ester group, a ketone group, an amino group, an amide group and a sulfur group.
Due to the structure that the polymer dewaxing agent is wrapped on the periphery of the nano magnetic core, the polymer dewaxing agent can be better contacted with crude oil, and the dewaxing effect is improved. The magnetic dewaxing agent can be separated by an external magnetic field, and the dewaxed crude oil can be separated from the precipitated wax and the residual dewaxing agent without separation operations such as centrifugation, so that the dewaxing process is simplified and the dewaxing cost is reduced.
Further, the magnetic nanoparticles are spherical magnetic nanoparticles. The magnetic nanoparticles 100 have a particle size of 5-50nm, e.g., 5nm, 10nm, 20nm, 30nm, 40nm, or 50nm, and the specific surface area per unit mass of the magnetic nanoparticles is larger as the particle size of the magnetic nanoparticles decreases. In order to provide a larger accommodating space for the polymer dewaxing agent and ensure that the polymer dewaxing agent can be fully stretched to play a dewaxing role, the particle size of the magnetic nanoparticles is 30 nm.
Further, the magnetic nanoparticles and the polymer dewaxing agent are compounded together by means of solution blending or melt blending. And coating the polymer dewaxing agent on the periphery of the magnetic nano particles by adopting a solution blending or melt blending mode so as to obtain the magnetic dewaxing agent. In order to reduce the use of solvent, the magnetic nanoparticles and the polymer dewaxing agent are compounded together by means of melt blending.
Further, the polymer dewaxing agent comprises polyacrylic acid high-carbon alcohol ester and/or polyethylene-vinyl acetate. Polyacrylic acid high-carbon alcohol ester and/or polyethylene-vinyl acetate are/is adopted as a polymer dewaxing agent and can be closely matched with the magnetic nanoparticles, so that the polymer dewaxing agent in the magnetic dewaxing agent is prevented from being separated from the magnetic nanoparticles in the using process. In order to obtain better dewaxing effect, the polymer dewaxing agent is a mixture of polyacrylic acid high-carbon alcohol ester and polyethylene-vinyl acetate. Of course, depending on the characteristics of the crude oil to be dewaxed, different polymeric dewaxed agents or combinations of polymeric dewaxed agents may be selected.
S200, mixing the magnetic dewaxing agent with the preset mass with the oil to be treated with the preset mass to obtain a mixture.
In the step S200, the magnetic dewaxing agent with a preset mass is mixed with the oil to be treated with a preset mass by using a mechanical stirring or magnetic stirring manner, so as to obtain a mixture. Further, when the preset mass of the oil product to be treated is 100g, the preset mass of the magnetic dewaxing agent is 5-20mg, that is, the mass ratio of the magnetic dewaxing agent to the oil product to be treated is 50-200mg/Kg, such as 50mg/Kg, 100mg/Kg, 150mg/Kg or 200 mg/Kg. Because the polymer dewaxing agent is coated on the periphery of the magnetic nano-particles, the magnetic dewaxing agent can be better mixed with the oil product to be treated and can play a dewaxing role to treat the oil product to be treated with the same quality, and the amount of the polymer dewaxing agent contained in the magnetic dewaxing agent is smaller than that of the polymer dewaxing agent used alone, so that the dewaxing cost is favorably reduced.
S300, cooling the mixture to a preset temperature or below to enable wax in the oil to be treated to be generated on the surface of the magnetic dewaxing agent, and obtaining the magnetic dewaxing agent containing precipitated wax.
In the step S300, under the condition of continuous stirring, the temperature of the mixture is reduced to below a preset temperature, so that the wax in the oil product to be treated is generated on the surface of the magnetic dewaxing agent. In one embodiment, the predetermined temperature may be 0-18 ℃, e.g., 0 ℃, 5 ℃, 10 ℃, 15 ℃ or 18 ℃, etc., and decreasing the temperature facilitates wax precipitation. For different types of oils to be treated, for example, oils to be treated with different environments or oils to be treated with different compositions such as water content, the wax precipitation conditions are different at the same temperature, so that the preset temperature is the wax precipitation point of the oils to be treated for better dewaxing effect. And when the temperature of the mixture is up to the wax precipitation point or below of the corresponding oil product to be treated, the wax in the oil product to be treated can be removed quickly and efficiently.
S400, applying a magnetic field to the mixture to precipitate the magnetic dewaxing agent.
In the step S400, since the magnetic dewaxing agent has a magnetic core, the magnetic dewaxing agent can be separated from the oil to be treated by applying a magnetic field. Of course, at least part of the separated magnetic dewaxing agent is the magnetic dewaxing agent containing precipitated wax. Further, the magnetic field is from a permanent magnet or an electromagnet. In order to reduce production costs and simplify the process, the magnetic field comes from a permanent magnet.
Further, due to the action of the magnetic field, the magnetic dewaxing agent cannot flow out along with the flowing of the liquid, and the dewaxed oil product to be treated can be separated from the magnetic dewaxing agent by simple pouring. In order to obtain higher separation efficiency, a magnetic field is applied to the mixture, and the method further comprises the following steps after the magnetic dewaxing agent is precipitated: the mixture is filtered and the magnetic dewaxing agent including precipitated wax is separated from the mixture.
In another embodiment, before the step of cooling the mixture to the preset temperature, the step of: heating the mixture to 50-80 ℃, and stirring for 0.2-1h by adopting a mechanical stirring mode. The adoption of stirring and heating modes is beneficial to fully mixing the magnetic dewaxing agent and the oil product to be treated and fully removing wax in the oil product to be treated.
The technical solution of the present invention will be further illustrated by the following examples, in the following implementation, the treatment method is mechanical stirring, after the temperature is reduced to the wax precipitation point, and the amount of the precipitated wax is not increased, the precipitated wax is separated according to the above method, and the dewaxing rate is calculated, and the dewaxing rate is the ratio of the mass of the precipitated wax to the measured wax content of the crude oil.
TABLE 1 comparison of the dewaxing effect of 1Kg of victory crude oil with 200mg of dewaxing agent
As can be seen from table 1, the magnetic dewaxing method can improve the dewaxing rate under the same type and amount of the dewaxing agent. The same dewaxing rate is achieved, and the dosage of the dewaxing agent can be reduced by adopting the magnetic dewaxing, so that the point cost is reduced.
TABLE 2 comparison of dewaxing effects on 1Kg of Tarim crude oil with 200mg of dewaxing agent
Comparing tables 1 and 2, it can be seen that when the amount of the polymer dewaxing agent is the same, the dewaxing effect can be further improved by using a combination of different dewaxing agents. That is, the dewaxing effect can be further improved by selecting the corresponding dewaxing agent for the same crude oil to be treated.
TABLE 3 comparison of the dewaxing effect of 1Kg of victory crude oil with 100mg of dewaxing agent
Comparing table 1 and table 3, it can be seen that the increase of the amount of the dewaxing agent is beneficial to the increase of the dewaxing rate when the crude oil to be treated with the same quality is treated.
TABLE 4 comparison of dewaxing effects on 1Kg of Tarim crude oil with 100mg of dewaxing agent
Similarly, comparing tables 2 and 4, it can be seen that the increase of the dosage of the dewaxing agent is beneficial to the increase of the dewaxing rate when the crude oil to be treated with the same quality is treated.
The comparison of the above examples shows that the magnetic dewaxing agent of the present invention can effectively increase the dewaxing rate and is advantageous to further reduce the dewaxing cost, compared with the use of the dewaxing agent alone.
In summary, the present invention discloses a magnetic dewaxing agent and a magnetic dewaxing method, wherein the magnetic dewaxing agent comprises magnetic nanoparticles and a polymer dewaxing agent coated on the peripheries of the magnetic nanoparticles; the magnetic nanoparticles comprise Fe3O4、γ-Fe2O3、Co2O3One or a combination of two or more of NiO; the polymer dewaxing agent comprises a high-molecular polymer with nonpolar groups and polar groups in molecules, including homopolymers and copolymers; the molecular weight of the polymer dewaxing agent is 4000-100000; the non-polar group comprises a long chain alkyl group, and the polar group comprises an ester group, a ketone group, an amino group, an amide group and a sulfur group. Through the mode, the dewaxing process can be simplified, and the dewaxing cost can be 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 (9)
1. A magnetic dewaxing agent, comprising:
the wax remover comprises magnetic nanoparticles and a polymer wax remover coated on the peripheries of the magnetic nanoparticles; the particle size of the magnetic nano-particles is 5-50 nm;
the magnetic nanoparticles comprise Fe3O4、γ-Fe2O3、Co2O3One or a combination of two or more of NiO;
the polymer dewaxing agent comprises a high-molecular polymer with nonpolar groups and polar groups in molecules, including homopolymers and copolymers; the molecular weight of the polymer dewaxing agent is 4000-100000; the non-polar group includes a long chain alkyl group and the polar group includes at least one of an ester group, a ketone group, an amino group, an amide group, or a thio group.
2. The magnetic dewaxing agent of claim 1, wherein the magnetic nanoparticles and the polymeric dewaxing agent are compounded by solution blending or melt blending.
3. The magnetic dewaxing agent of claim 1, wherein the polymeric dewaxing agent comprises a polyacrylic acid higher alcohol ester and/or polyethylene vinyl acetate.
4. A magnetic dewaxing method, comprising:
providing a magnetic dewaxing agent with preset mass, wherein the magnetic dewaxing agent comprises magnetic nanoparticles and a polymer dewaxing agent coated on the peripheries of the magnetic nanoparticles, and the particle size of the magnetic nanoparticles is 5-50 nm; the magnetic nanoparticles comprise Fe3O4、γ-Fe2O3、Co2O3One or a combination of two or more of NiO; the polymer dewaxing agent comprises a high-molecular polymer with nonpolar groups and polar groups in molecules, including homopolymers and copolymers; the molecular weight of the polymer dewaxing agent is 4000-100000; the non-polar group comprises a long chain alkyl group, and the polar group comprises at least one of an ester group, a ketone group, an amino group, an amide group or a sulfur group;
mixing the magnetic dewaxing agent with the preset mass with the oil to be treated with the preset mass to obtain a mixture;
cooling the mixture to a preset temperature or below to crystallize the wax on the surface of the magnetic dewaxing agent to obtain a magnetic dewaxing agent containing precipitated wax;
and applying a magnetic field to the mixture to precipitate the magnetic dewaxing agent containing the precipitated wax.
5. The method according to claim 4, characterized in that the magnetic dewaxing agent with the preset mass is 5-20mg when the oil to be treated with the preset mass is 100 g.
6. The method according to claim 4, characterized in that the preset temperature is the wax appearance point of the oil to be treated.
7. The method of claim 4, wherein the step of cooling the mixture to the predetermined temperature further comprises:
heating the mixture to 50-80 ℃, and stirring for 0.2-1h by adopting a mechanical stirring mode.
8. The method of claim 4, wherein applying a magnetic field to the mixture to cause the magnetic dewaxing agent to precipitate further comprises:
the mixture is filtered and the magnetic dewaxing agent including precipitated wax is separated from the mixture.
9. The method of claim 4, wherein the magnetic field is from a permanent magnet or an electromagnet.
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| CN1639212A (en) * | 2002-03-01 | 2005-07-13 | 罗麦斯添加剂有限公司 | Copolymers as dewaxing additives |
| CN103339234A (en) * | 2011-02-09 | 2013-10-02 | 赢创油品添加剂有限公司 | Method for dewaxing mineral oil compositions |
| CN105112090A (en) * | 2015-09-06 | 2015-12-02 | 中国石油天然气股份有限公司 | Oil wax separating agent, preparation method thereof and oil wax separating method |
| CN105152841A (en) * | 2015-09-25 | 2015-12-16 | 中北大学 | Low-temperature-freezing magnetic separation method and device for long-chain alkene and long-chain alkane mixture |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639212A (en) * | 2002-03-01 | 2005-07-13 | 罗麦斯添加剂有限公司 | Copolymers as dewaxing additives |
| CN103339234A (en) * | 2011-02-09 | 2013-10-02 | 赢创油品添加剂有限公司 | Method for dewaxing mineral oil compositions |
| CN105112090A (en) * | 2015-09-06 | 2015-12-02 | 中国石油天然气股份有限公司 | Oil wax separating agent, preparation method thereof and oil wax separating method |
| CN105152841A (en) * | 2015-09-25 | 2015-12-16 | 中北大学 | Low-temperature-freezing magnetic separation method and device for long-chain alkene and long-chain alkane mixture |
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