CN114437760B - Dewaxing method for raw oil - Google Patents
Dewaxing method for raw oil Download PDFInfo
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- CN114437760B CN114437760B CN202011190492.7A CN202011190492A CN114437760B CN 114437760 B CN114437760 B CN 114437760B CN 202011190492 A CN202011190492 A CN 202011190492A CN 114437760 B CN114437760 B CN 114437760B
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000002904 solvent Substances 0.000 claims abstract description 119
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920001971 elastomer Polymers 0.000 claims abstract description 42
- 239000005060 rubber Substances 0.000 claims abstract description 42
- 238000002425 crystallisation Methods 0.000 claims abstract description 40
- 230000008025 crystallization Effects 0.000 claims abstract description 40
- 238000011282 treatment Methods 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 29
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 239000005453 ketone based solvent Substances 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 125
- 239000001993 wax Substances 0.000 description 27
- 238000010790 dilution Methods 0.000 description 18
- 239000012895 dilution Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 13
- 150000002576 ketones Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000007670 refining Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 125000005605 benzo group Chemical group 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- TXHIDIHEXDFONW-UHFFFAOYSA-N benzene;propan-2-one Chemical compound CC(C)=O.C1=CC=CC=C1 TXHIDIHEXDFONW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LHRCREOYAASXPZ-UHFFFAOYSA-N dibenz[a,h]anthracene Chemical compound C1=CC=C2C(C=C3C=CC=4C(C3=C3)=CC=CC=4)=C3C=CC2=C1 LHRCREOYAASXPZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- SREWXRJITRVXSM-UHFFFAOYSA-N propan-2-one;prop-1-ene Chemical group CC=C.CC(C)=O SREWXRJITRVXSM-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
Abstract
The invention provides a raw oil dewaxing method, which comprises the following steps: the raw oil and the compound solvent are mixed and then subjected to crystallization dewaxing treatment to obtain wax crystals and dewaxed oil respectively; crystallizing the wax to form a liquid state, and then performing desolventizing treatment to obtain rubber oil; wherein the complex solvent comprises furfural and ketone solvents. The raw oil dewaxing method provided by the invention has higher dewaxing efficiency, and can simultaneously coproduce rubber oil and improve the yield of rubber oil products.
Description
Technical Field
The invention relates to the field of dewaxing raw oil treatment, in particular to a raw oil dewaxing method.
Background
In the petroleum processing and production process, the petroleum fraction contains long-chain normal paraffins (known as waxes) which can affect the processing and production or downstream use, for example, in the production process of lubricating oil, at a lower temperature, the waxes can wrap around surrounding lubricating oil components to be separated out to form a network structure, and the fluidity of the lubricating oil is affected, so dewaxing is an indispensable step in the processing and production process of petroleum products such as lubricating oil.
The crystallization dewaxing is a process of reducing the solidifying point of lubricating oil by removing wax which has been precipitated by filtration by utilizing the property that wax can be crystallized from a solution at a low temperature, and belongs to such methods as cold press dewaxing, centrifugal dewaxing, solvent dewaxing and the like, wherein the solvent dewaxing mainly comprises ketobenzene dewaxing, propane dewaxing, acetone-propylene dewaxing, dilute cold dewaxing and the like, and is also a common dewaxing process.
In 1927, indiana refineries established the world's first set of solvent dewaxing units using acetone-benzene as the solvent system; in 1932, the mobil oil company developed the earliest propane dewaxing technology, however, because of the poor selectivity of propane, its development and application was limited; in 1934, the Texaco solvent dewaxing process is developed, methyl ethyl ketone is adopted to replace acetone, toluene is adopted to replace benzene, the process has strong adaptability to raw materials, process parameters can be adjusted according to the characteristics of different raw materials, most of the currently used solvent dewaxing processes refer to the Texaco solvent dewaxing process, and the number of the process devices is about 120, and the process devices account for more than 80% of the solvent dewaxing devices; in 1940, canadian empire petroleum company developed a first set of higher ketone dewaxing process units mainly using methyl n-propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, etc. higher ketone as dewaxing solvent (i.e. single solvent is adopted), however, the higher ketone solvent contains some larger hydrocarbon groups, which increase the solubility of oil therein, and the higher ketone is adopted as dewaxing solvent, the dewaxing temperature difference is generally 0 to 2 ℃, the molecular weight of the higher ketone is large, and the low temperature viscosity increase often causes filtration difficulty; the exxon company developed a thin cold dewaxing process in the twentieth century, the core device of which was a thin cold tower (crystallizer), however, the process also had the disadvantages of large solvent ratio, low diluent temperature, high energy consumption, and the like. In the prior art, the ketobenzene dewaxing process is widely researched and focused, the basic principle is mainly to crystallize and separate out crystals by utilizing the different dissolving capacities of solvents on oil and wax and the dissolving and dispersing actions of solvents on oil and wax, and then filtering and separating are carried out, more specifically, in the ketobenzene dewaxing process, the solvent is usually used for diluting at each dilution point in the crystallization process, and in the filtering process, cold washing is carried out at each cold washing point, and at present, the dilution mode adopts a 3-point or 4-point dilution mode.
The solvents used in the prior ketobenzene dewaxing process are generally binary mixed solvents of ketone (such as methyl ethyl ketone, butanone and the like) -toluene, the toluene can dissolve oil and wax, the ketone solvents such as butanone and the like can gather wax, the two solvents have different effects, the mixed solvents generally have different effect characteristics under different mixing ratios, and the optimal mixing ratio often needs to be inspected in actual production. However, the dewaxing efficiency of the current dewaxing process is still further improved, although the dewaxing process can remove the wax in the raw oil to some extent. On the other hand, aromatic extract oil (Distillates aromatic extraction, DAE) of the vacuum fraction is generally mainly extract oil (called reverse-order extract oil) produced by a reverse-order process of solvent dewaxing-solvent refining in a production process of lubricating oil base oil, and high-condensation-point wax components in the oil can be removed by dewaxing treatment-solvent refining, and the content of saturated hydrocarbon (especially paraffin) in the obtained reverse-order extract oil is generally less than 30%. The pour point of the reverse order extract oil is generally about 0 ℃, and the reverse order extract oil can be used as styrene butadiene rubber filling oil.
Environmental requirements are becoming increasingly stringent, for example, european Union EC1907/2006 has clearly limited tricyclic and more polycyclic aromatic hydrocarbons (polycylic aromatics, abbreviated as PCA, measured by the British Petroleum institute method IP 346) in oils such as rubber oils to less than 3% by mass and benzo (a) pyrene content of not more than 1mg/kg, benzo (a) anthracene,The total content of eight specific Polycyclic Aromatic Hydrocarbons (PAHs) including benzo (b), benzo (j), benzo (k), benzo (a), benzo (e) pyrene and dibenzo (a, h) anthracene is not more than 10mg/kg, and the environment-friendly aromatic rubber oil meets the environmental-friendly index requirements and is called environment-friendly aromatic rubber oil, and the environment-friendly aromatic rubber oil is gradually becoming the research and development direction.
At present, rubber oil is mainly prepared by adopting a solvent extraction mode, for example, patent document CN101684185A discloses a production method of high aromatic environment-friendly rubber oil, light hydrocarbon and raw oil are mixed, then enter an extraction tower, and are extracted and refined with a methyl pyrrolidone, phenol or furfural solvent in the extraction tower, and the refined solution is subjected to solvent recovery to obtain environment-friendly rubber oil; CN103725317a discloses a method for producing aromatic rubber filling oil, which comprises mixing raw oil with C6-C12 light alkane, extracting with solvent, optionally, recycling a part of extracted oil back to an extraction tower to dissolve dewaxing auxiliary agent in the raffinate oil obtained in the step, and then performing solvent dewaxing, wherein the dewaxing auxiliary agent is one or more of petroleum paraffin, petroleum microcrystalline wax and synthetic paraffin; CN103242901a discloses a rubber oil and a preparation method thereof, the proposal takes naphthenic distillate oil and deasphalted oil as raw materials, and carries out two-stage solvent extraction to prepare the rubber oil (secondary extraction oil); WO9844075 discloses a method for selectively re-extracting aromatic hydrocarbon oil by solvent, which can prepare environment-friendly aromatic hydrocarbon oil by taking extracted oil in the refining process of lubricating oil solvent as raw material and dimethyl sulfoxide (DMSO) as solvent.
By adopting the solvent extraction mode, the defects of high viscosity of extracted oil, blockage of the filling material of the extraction tower, low product yield (most of the product is not more than 40 wt%) and the like generally exist, so the practical application is limited. Therefore, optimizing the preparation method of rubber oil, improving the comprehensive properties such as environmental protection and the yield thereof is an important subject faced by the person skilled in the art.
Disclosure of Invention
The invention provides a raw oil dewaxing method, which has higher dewaxing efficiency, can co-produce rubber oil and improve the yield of the rubber oil, and can overcome the defects in the prior art.
The invention provides a raw oil dewaxing method, which comprises the following steps: the raw oil and the compound solvent are mixed and then subjected to crystallization dewaxing treatment to obtain wax crystals and dewaxed oil respectively; crystallizing the wax to form a liquid state, and then performing desolventizing treatment to obtain rubber oil; wherein the complex solvent comprises furfural and ketone solvents.
According to the raw oil dewaxing method provided by the invention, the raw oil is subjected to crystallization dewaxing treatment by adopting the composite solvent (namely a furfural/ketone double-solvent system), so that the dewaxing efficiency is higher, meanwhile, the rubber oil can be coproduced, the yield of the rubber oil is higher, and research results show that the yield of the rubber oil is not lower than 50wt% and even higher than 55wt% by the dewaxing method provided by the invention, the prepared rubber oil meets the environmental protection requirement, the PCA content is less than 3%, and the total content of 8PAHs (8 polycyclic aromatic hydrocarbons) is less than 10mg/kg, so that the raw oil dewaxing method is a high-quality environmental-friendly rubber oil product. The inventor considers that furfural is soluble to aromatic hydrocarbon, can realize concentration and separation of aromatic hydrocarbon components in raw oil, introduces ketone solvents (almost insoluble to oil/hydrocarbon components) and cooperates with the aromatic hydrocarbon components, so that the selectivity in the crystallization dewaxing treatment process can be improved, and the yield of refined oil (namely the rubber oil) is greatly improved.
The present invention may employ conventional ketone solvents in the art, such as conventional lower ketones having no more than 4 carbon atoms or higher ketones having a carbon number greater than 4 or mixtures of both, and in some preferred embodiments, the ketone solvents may generally comprise butanone. The solidifying point of the furfural is-36.5 ℃, the polycyclic aromatic hydrocarbon can be dissolved, and after the polycyclic aromatic hydrocarbon is dissolved, good fluidity (similar to the fluidity at room temperature) can be kept at-30 ℃, and the solidifying point of the butanone is-86 ℃, so that the composite solvent formed by the two components can still keep very good fluidity and completely mutually dissolve at the crystallization temperature (such as-30 ℃ to-45 ℃ or-30 ℃ to-35 ℃) and the dewaxing treatment efficiency can be further ensured to be improved.
According to the research of the invention, in the composite solvent, the volume fraction of furfural can be 89-99%, and the volume fraction of ketone solvent can be 1-11%, which is beneficial to improving dewaxing efficiency and quality and yield of rubber oil.
Through further researches, the mass ratio of the composite solvent to the raw oil can be 2-10:1, and further can be 2-9:1 or 2-8:1 or 2-7:1 or 2-6:1 or 2-5:1 or 2-4:1.
In the present invention, the raw oil may be a furfural extract oil (which may be generally referred to as a naphthenic aromatic hydrocarbon oil) of naphthenic Distillate (DAE), and may be a furfural extract oil of a vacuum distillate of naphthenic distillate, which has a distillation range of 300 to 520 ℃. Specifically, the raw oil may be furfural extract oil or the like prepared by vacuum distillate of naphthenic distillate through conventional processes in the field such as hydrogenation deacidification, solvent deacidification-furfural refining, and the raw oil may be at least one of three-wire reduced furfural extract oil and four-wire reduced furfural extract oil.
In the aspect of rubber oil production, since the polycyclic aromatic hydrocarbon and other aromatic hydrocarbons in the DAE raw material are in symbiotic relation, if the conventional secondary extraction process is adopted to produce or prepare the environment-friendly rubber oil, extraction solvents such as furfural are generally required to be utilized, the effect that the polycyclic aromatic hydrocarbon is lower and other non-polycyclic aromatic hydrocarbon components are kept as much as possible is difficult to obtain by the adjustment means of the conventional furfural refining process and the like, and the yield of refined oil (rubber oil product) is usually not more than 50wt%, and the implementation of the invention can effectively overcome the defect and can obviously improve the yield of the environment-friendly rubber oil product.
Specifically, the raw oil and the compound solvent may be mixed and then subjected to cooling crystallization, and in one embodiment of the present invention, the crystallization temperature may be-40 ℃ to-30 ℃, and further may be-35 ℃ to-30 ℃ during the crystallization dewaxing treatment. In general, most of cycloalkyl aromatic oil (such as reduced-three-wire/reduced-four-wire furfural extract oil) components are in a solidification state at a temperature of between 40 ℃ below zero and 30 ℃ below zero, and the crystallization treatment is carried out at the low temperature, so that precipitation and crystallization of wax components are facilitated, and the yield and quality of rubber oil are improved.
Further, in the crystallization dewaxing treatment process, the crystallization time is generally not less than 30min, for example, may be 30min to 240min, preferably 60min to 180min, and in a specific implementation, the mixed system formed by mixing the raw oil and the composite solvent may be cooled at the crystallization temperature (for example, the temperature is between-40 ℃ and-30 ℃ or between-35 ℃ and-30 ℃) for not less than 30min. In the cold insulation process, slow stirring can be matched to ensure that the temperature of the whole mixed system is uniform and stable, after the cold insulation is finished, stirring can be stopped, and standing and sedimentation are continued for a period of time at the crystallization temperature, for example, 30+/-10 minutes, so that the separation of wax crystallization and dewaxed oil (such as subsequent filtration and other treatments) is facilitated.
In a preferred embodiment of the present invention, the compound solvent may be added to the raw oil in multiple times, after each addition, a cooling treatment is performed on the system containing the compound solvent and the raw oil, and after all the compound solvents are added, the obtained mixed system is cooled to-40 ℃ to-30 ℃ to perform the crystallization, in this manner, the compound solvent is adopted to perform stepwise dilution cooling (or stepwise dilution cooling) on the raw oil, so that the quality and yield of the rubber oil can be further improved; wherein, the cooling rate can be 25+/-5 ℃/h.
Further, the complex solvent may be added to the raw oil 2 to 6 times.
In a preferred embodiment, the mass ratio (or dilution ratio) of the complex solvent to the feedstock oil added each time is greater than 0.5:1, for example, may be 0.5 to 1.5, and further may be 0.5 to 1.0 or 0.75 to 1.0.
In the specific implementation, after the compound solvent is added each time, stirring can be performed to accelerate the mixing of the compound solvent and the raw oil system, then the obtained system can be kept stand (settled) for about 20-40min, and then cooling treatment is performed, so that the process is favorable for improving the yield and quality of the rubber oil, and presumably, the reason is that the compound solvent is adopted to perform the gradual cooling treatment on the raw oil, and in the settling process after the compound solvent is added each time, some ideal wax components may be crystallized and separated out.
In an embodiment of the present invention, in the step-wise dilution and cooling process of the raw oil with the compound solvent, the compound solvent may be used to dilute the raw oil at the same temperature, that is, the temperature of the compound solvent to be added is the same as the temperature of the raw oil system to be mixed with the compound solvent to be added, specifically, the compound solvent may be divided into n portions and added into the raw oil n times; the method comprises the steps of enabling the temperature of raw oil to be the same as the temperature of a 1 st part of compound solvent, adding the 1 st part of compound solvent into the raw oil, then carrying out cooling treatment on an obtained 1 st system, reducing the temperature to be 1 st dilution temperature, then controlling the temperature of a 2 nd part of compound solvent to be equal to the 1 st dilution temperature, adding the 2 nd part of compound solvent into the 1 st system, carrying out cooling treatment on the obtained 2 nd system, reducing the temperature to be 2 nd dilution temperature … …, controlling the temperature of an n-th part of compound solvent to be equal to the n-1 st dilution temperature, adding the n-th part of compound solvent into the n-1 st system, carrying out cooling treatment on the obtained n-th system (namely a mixed system formed by adding all the compound solvents into the raw oil), reducing the crystallization temperature to (-40 ℃ to-30 ℃ or-35 ℃ to-30 ℃), and then carrying out cold preservation and crystallization; where n=2-6, the complex solvent may be equally divided into n portions (i.e., the amount of complex solvent per 1 portion is equal).
In general, the gradual dilution and cooling (i.e., the completion of the charging) of the raw oil by the complex solvent may be completed within a range of 60 ℃ to-25 ℃, that is, the temperature of the raw oil and the part 1 complex solvent may be 60 ℃ and the temperature of the part n complex solvent may be-25 ℃.
Of course, the temperature of the raw oil is not limited to 60 ℃, and can be 40-70 ℃ generally, for example, 50-60 ℃ or 45-60 ℃, so that the precipitation of components such as wax in the raw oil can be prevented, and the mixing of the raw oil and the composite solvent can be prevented.
Further, after the crystallization dewaxing treatment, the obtained mixed feed liquid suspending the wax crystals can be filtered to obtain wax crystals and dewaxed oil; wherein, the temperature of the filtration can be-35 ℃ to-25 ℃; the filtration may specifically be vacuum filtration.
The wax crystal is mainly in the form of a cerate (non-liquid state) at the crystallization-filtration temperature, and is generally formed into a liquid state under the room temperature condition, and because of entrainment, the wax crystal generally contains part of a composite solvent, and the final environment-friendly rubber oil product is obtained after the solvent removal treatment. The complex solvent in the wax crystals may be removed by distillation method generally according to the boiling point of butanone (79.6 ℃) and the boiling point of furfural (161.4 ℃), and specifically, in an embodiment of the present invention, the above-mentioned process of desolventizing treatment may include: performing normal pressure distillation or reduced pressure distillation on the liquid state formed by wax crystallization, and removing the solvent in the liquid state to obtain rubber oil;
the invention can adopt the conventional method in the field to carry out the normal pressure distillation or the reduced pressure distillation, in particular, in the reduced pressure distillation process, the residual pressure of the system can be about 100mmHg when the temperature of the distillation outlet of the pressurizing system is equal to more than 161 ℃ of the normal pressure temperature, and when the liquid phase temperature reaches 190-200 ℃, the solvent including butanone and furfural can be considered to be completely removed, then the liquid phase after the solvent removal is cooled to 80-100 ℃, the vacuum breaking and the emptying are carried out, and the liquid phase product is taken out, thus obtaining the environment-friendly rubber oil.
The invention can adopt the conventional continuous/intermittent dewaxing industrial device or experimental device in the field to carry out the dewaxing treatment, such as the conventional ketobenzene dewaxing industrial device or experimental device consisting of a crystallization system, a freezing system, a vacuum filtration system and a solvent recovery system, and the like, and can also carry out the treatment such as feeding according to the working procedure of conventional ketobenzene dewaxing during specific operation, and the details are not repeated.
The implementation of the invention has at least the following beneficial effects:
according to the crude oil dewaxing method, the composite solvent formed by the furfural and the ketone solvent is adopted to carry out crystallization dewaxing treatment on the raw oil, so that the wax component in the raw oil can be effectively removed, the influence of the existence of wax on the subsequent production of the raw oil is solved, meanwhile, the environment-friendly rubber oil product is coproduced, the yield of the environment-friendly rubber oil product can be improved, and the method has important practical significance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
in this embodiment, a conventional continuous dewaxing system with structures such as solvent dilution and distribution, raw material/solvent mixing, solvent (diluent) cooling (jacket type), and mixed material cooling crystallization (jacket type) is adopted to perform dewaxing treatment on raw oil, and in the dewaxing process, the temperature reduction/heating/heat preservation can be controlled by a system temperature increase/temperature reduction program, specifically, the cooling treatment can be performed by a cooling medium forced circulation mode, and the like, which is not described again.
In the embodiment, the composite solvent is divided into n parts and added into the raw oil for n times, and the process is specifically as follows:
feeding raw oil into a crystallization tank, and preserving heat to 45-60 ℃; heating the composite solvent in a cooling tank (with a cooling jacket, an electric stirring paddle, a lower discharge port and an upper feed port) to the heat preservation temperature of the raw oil, adding a part of the composite solvent (namely, part 1 of the composite solvent) into a crystallization tank, mixing the composite solvent with the raw oil under stirring, stopping stirring, standing for 30min, and then starting stirring and cooling to reduce the temperature of the obtained system 1 to the dilution temperature 1; cooling the rest part of the compound solvent in the cooling tank to 0 ℃, adding a part of the compound solvent (part 2 of the compound solvent) into the crystallization tank, mixing the compound solvent with the 1 st system under stirring, stopping stirring, standing for 30min, starting stirring and cooling down to enable the temperature of the obtained 2 nd system to be reduced to the 2 nd dilution temperature … …, cooling the rest part of the compound solvent in the cooling tank to the n-1 th dilution temperature, adding the n-1 st compound solvent into the crystallization tank, mixing the n-1 st compound solvent with the n-1 st system under stirring, stopping stirring, standing for 30min, starting stirring and cooling down to enable the n-th system (namely a mixed system formed by adding all the compound solvent into raw oil) to be reduced to the crystallization temperature (-40 ℃ to-30 ℃ or-35 ℃ to-30 ℃), and then preserving cold for crystallization; wherein, n=2-6, the cooling rate in the cooling process is 25 ℃/h; equally dividing the composite solvent into n parts (i.e. the amount of composite solvent is equal for every 1 part);
after the cold insulation crystallization is finished, obtaining mixed material liquid with suspended wax crystals; introducing the mixed feed liquid into a freezer through a cold insulation pipeline, and carrying out vacuum suction filtration on the mixed feed liquid to obtain filtrate (namely dewaxed oil) and wax crystals; wherein, the temperature of the refrigerator is controlled to be vacuum filtration temperature (namely minus 35 ℃ to minus 25 ℃), and before the filtration, the filter paper, the Buchner funnel, the filter flask and the like are all kept at the constant temperature/precooled for 1h in the refrigerator at minus 35 ℃ to minus 25 ℃;
and (3) carrying out reduced pressure distillation on wax crystals to remove the entrained composite solvent, wherein the residual pressure of the system is 100mmHg during the reduced pressure, when the temperature of a distillation outlet is equivalent to more than 161 ℃ of normal pressure temperature and the liquid phase temperature reaches 200 ℃, the solvent including butanone and furfural can be considered to be completely removed, then cooling the liquid phase after the solvent removal to 90 ℃, breaking vacuum and emptying, and taking out the liquid phase product, namely the environment-friendly rubber oil.
In accordance with the procedure described above, three aromatic hydrocarbon extract oils A, B, C were subjected to dewaxing treatment, the properties of A, B, C are shown in table 1, with a dewaxing treatment test for a being test 1a, B being test 1B, and C being test 1C;
in the test 1a, the test 1b, the test 1c, the test conditions such as the composition of the composite solvent, the mass ratio of the composite solvent to the raw oil (solvent ratio in table 1), the mass ratio of the amount of the composite solvent added per 1 part to the raw oil (dilution ratio in table 1), the number of dilution stages (i.e., the value of n), the cold retention temperature (i.e., crystallization temperature), the cold retention time, the vacuum filtration temperature, the vacuum filtration time, and the yield of the environment-friendly rubber oil are shown in table 2, and the physical properties of the obtained environment-friendly rubber oil are shown in table 3.
TABLE 1 oil Properties of raw materials
Table 2 test conditions
TABLE 3 physical Properties of rubber oil
Claims (17)
1. A process for dewaxing a feed oil comprising: the raw oil and the compound solvent are mixed and then subjected to cooling crystallization dewaxing treatment to obtain wax crystals and dewaxed oil respectively; crystallizing the wax to form a liquid state, and then performing desolventizing treatment to obtain rubber oil; wherein the composite solvent comprises furfural and butanone, and the mass ratio of the composite solvent to the raw oil is 2-10:1.
2. The dewaxing method according to claim 1, wherein in the composite solvent, the volume fraction of furfural is 89-99% and the volume fraction of butanone is 1-11%.
3. The dewaxing process of claim 1, wherein the mass ratio of complex solvent to feed oil is from 2 to 4:1.
4. A dewaxing process according to claim 1 or 3 characterised in that the feed oil comprises a furfural extract of naphthenic distillate oil having a distillation range of 300-520 ℃.
5. The dewaxing method according to claim 1, wherein the crystallization temperature during the crystallization dewaxing treatment is-40 ℃ to-30 ℃.
6. The dewaxing method of claim 5, wherein the crystallization time is not less than 30 minutes.
7. The dewaxing method according to any one of claims 1, 5 and 6, wherein the composite solvent is added to the raw oil in a plurality of times, the system containing the composite solvent and the raw oil is subjected to a cooling treatment after each addition, and the mixed system obtained after the addition of the whole composite solvent is cooled to-40 ℃ to-30 ℃ to carry out the crystallization.
8. The dewaxing method of claim 7, wherein the rate of temperature reduction is 25±5 ℃/h.
9. The dewaxing process according to claim 7, wherein the complex solvent is added to the feed oil 2 to 6 times.
10. The dewaxing process according to claim 8, wherein the complex solvent is added to the feed oil 2 to 6 times.
11. The dewaxing process of claim 7 wherein the mass ratio of composite solvent to feed oil per addition is greater than 0.5:1.
12. the dewaxing process of claim 8 wherein the mass ratio of composite solvent to feed oil per addition is greater than 0.5:1.
13. the dewaxing process of claim 9 wherein the mass ratio of composite solvent to feed oil per addition is greater than 0.5:1.
14. the dewaxing process according to claim 10 wherein the mass ratio of the composite solvent to the feed oil per addition is greater than 0.5:1.
15. the dewaxing method according to any one of claims 1, 5 and 6, wherein after the crystallization dewaxing treatment, the obtained mixed feed liquid is filtered to obtain wax crystals and dewaxed oil; wherein the temperature of the filtration is-35 ℃ to-25 ℃.
16. The dewaxing method of claim 15, wherein the filtering is vacuum filtration.
17. The dewaxing method of claim 1, wherein the process of desolventizing treatment comprises: and (3) performing normal pressure distillation or reduced pressure distillation on the liquid state formed by wax crystallization, and removing the solvent in the liquid state to obtain the rubber oil.
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| GB679173A (en) * | 1947-06-24 | 1952-09-17 | Texaco Development Corp | Improvements in or relating to the separation of wax from hydrocarbon mixtures |
| CN103725317A (en) * | 2012-10-16 | 2014-04-16 | 中国石油化工股份有限公司 | Production method of filling distillate aromatic extract |
| CN105838419A (en) * | 2015-01-12 | 2016-08-10 | 中国石油化工股份有限公司 | Preparation method of aromatic hydrocarbon rubber oil |
| CN106929100A (en) * | 2015-12-29 | 2017-07-07 | 中国石油化工股份有限公司 | A kind of preparation method of aromatic rubber oil |
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| GB679173A (en) * | 1947-06-24 | 1952-09-17 | Texaco Development Corp | Improvements in or relating to the separation of wax from hydrocarbon mixtures |
| CN103725317A (en) * | 2012-10-16 | 2014-04-16 | 中国石油化工股份有限公司 | Production method of filling distillate aromatic extract |
| CN105838419A (en) * | 2015-01-12 | 2016-08-10 | 中国石油化工股份有限公司 | Preparation method of aromatic hydrocarbon rubber oil |
| CN106929100A (en) * | 2015-12-29 | 2017-07-07 | 中国石油化工股份有限公司 | A kind of preparation method of aromatic rubber oil |
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