CN114437760A - Raw oil dewaxing method - Google Patents
Raw oil dewaxing method Download PDFInfo
- Publication number
- CN114437760A CN114437760A CN202011190492.7A CN202011190492A CN114437760A CN 114437760 A CN114437760 A CN 114437760A CN 202011190492 A CN202011190492 A CN 202011190492A CN 114437760 A CN114437760 A CN 114437760A
- Authority
- CN
- China
- Prior art keywords
- oil
- solvent
- dewaxing
- temperature
- crystallization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 116
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 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 38
- 239000005060 rubber Substances 0.000 claims abstract description 38
- 238000002425 crystallisation Methods 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 32
- 150000002576 ketones Chemical class 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims description 27
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- 239000003921 oil Substances 0.000 description 122
- 239000001993 wax Substances 0.000 description 26
- 238000010790 dilution Methods 0.000 description 16
- 239000012895 dilution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 238000007710 freezing Methods 0.000 description 7
- 230000008014 freezing Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 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 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000010692 aromatic oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000005453 ketone based solvent Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 3
- KHNYNFUTFKJLDD-UHFFFAOYSA-N Benzo[j]fluoranthene Chemical compound C1=CC(C=2C3=CC=CC=C3C=CC=22)=C3C2=CC=CC3=C1 KHNYNFUTFKJLDD-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- TXHIDIHEXDFONW-UHFFFAOYSA-N benzene;propan-2-one Chemical compound CC(C)=O.C1=CC=CC=C1 TXHIDIHEXDFONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000000243 solution Substances 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
- 101100134058 Caenorhabditis elegans nth-1 gene Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HAXBIWFMXWRORI-UHFFFAOYSA-N Benzo[k]fluoranthene Chemical compound C1=CC(C2=CC3=CC=CC=C3C=C22)=C3C2=CC=CC3=C1 HAXBIWFMXWRORI-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
- 239000002199 base oil Substances 0.000 description 1
- FTOVXSOBNPWTSH-UHFFFAOYSA-N benzo[b]fluoranthene Chemical compound C12=CC=CC=C1C1=CC3=CC=CC=C3C3=C1C2=CC=C3 FTOVXSOBNPWTSH-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 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
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 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
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 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
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: mixing raw oil with a composite solvent, and then carrying out crystallization and dewaxing treatment to respectively obtain wax crystals and dewaxed oil; carrying out desolventizing treatment after the wax is crystallized to form a liquid state, so as to obtain rubber oil; wherein the composite solvent comprises furfural and a ketone solvent. The raw oil dewaxing method provided by the invention has higher dewaxing efficiency, and can be used for co-producing rubber oil and improving 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 process of petroleum processing and production, the petroleum fraction contains long-chain normal paraffin (so-called wax) which affects the processing and production or downstream use of the petroleum fraction, for example, in the process of lubricant oil production, at a low temperature, the wax can wrap the surrounding lubricant oil components to be separated out to form a network structure, and the fluidity of the lubricant oil is affected, so that dewaxing is an essential step in the process of petroleum oil processing and production such as lubricant oil.
The crystal dewaxing is a process of lowering the freezing point of a lubricating oil by removing a wax precipitated by filtration by utilizing the property that the wax can be crystallized and precipitated from a solution at a low temperature, and includes mainly cold-pressing dewaxing, centrifugal dewaxing, solvent dewaxing and the like, and the solvent dewaxing mainly includes ketone benzene dewaxing, propane dewaxing, acetone-propylene dewaxing, dilute cold dewaxing and the like, and is also a common dewaxing process.
In 1927, indiana oil refining company in the united states built the world's first solvent dewaxing unit, which used acetone-benzene as the solvent system; in 1932, Mobil oil company developed the earliest propane dewaxing techniques, however, due to the poor selectivity of propane, its development and application were limited; in 1934, a Texaco solvent dewaxing process is disclosed, which adopts methyl ethyl ketone to replace acetone and toluene to replace benzene, has stronger adaptability to raw materials, can adjust process parameters according to the characteristics of different raw materials, mostly uses the Texaco solvent dewaxing process for reference, and has about 120 sets of process devices which account for more than 80 percent of solvent dewaxing devices; in 1940, the canadian empire oil company developed a first set of advanced ketone dewaxing process apparatus, which mainly uses advanced ketones such as methyl n-propyl ketone, methyl isopropyl ketone and methyl isobutyl ketone as dewaxing solvents (i.e. a single solvent is used), however, such advanced ketone solvents contain some larger hydrocarbon groups, which can increase the solubility of oil therein, and the advanced ketone solvents have dewaxing temperature difference of generally 0 to 2 ℃ and high molecular weight, and the increase of low-temperature viscosity of the advanced ketone often causes filtration difficulty; the exxon company developed the dilute cooling dewaxing process in the sixth and seventies of the twentieth century, and the core device of the dilute cooling process was a dilute cooling tower (crystallizer), but the process also has the defects of large solvent ratio, low diluent temperature, high energy consumption and the like. At present, the ketone-benzene dewaxing process is widely researched and focused, and the basic principle is mainly to utilize the different dissolving capacities of the solvent to the oil and the wax and the dissolving and dispersing effects of the solvent to the oil and the wax to crystallize the wax and precipitate crystals, and then to perform filtration and separation, more specifically, in the ketone-benzene dewaxing process, the solvent is usually used to dilute at each dilution point in the crystallization process, and the cold wash is performed at each cold wash point in the filtration process, and at present, the 3-point or 4-point dilution mode is mostly adopted.
The solvent used in the prior ketobenzene dewaxing process is generally a binary mixed solvent of ketone (such as methyl ethyl ketone, butanone and the like) -toluene, the toluene can dissolve oil and wax, the ketone solvent such as butanone and the like can gather wax, the two solvents have different effects, the mixed solvent generally shows different effect characteristics under different mixing ratios, and the optimal mixing ratio is usually required to be observed in actual production. However, although the dewaxing efficiency of the conventional dewaxing process can remove wax from the feedstock oil to some extent, the dewaxing efficiency is still to be further improved. On the other hand, the aromatic extract oil (DAE) of the vacuum distillate is mainly an extract oil (called reverse-order extract oil) produced by the reverse-order flow of solvent dewaxing-solvent refining in the production process of lubricant base oil, and wax components with high pour point in oil products can be removed by dewaxing treatment-solvent refining, and the content of saturated hydrocarbons (especially paraffin hydrocarbons) 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 protection requirements have become increasingly strict, for example, European Union EC1907/2006 has clearly limited that the mass fraction of tricyclic and higher polycyclic aromatic hydrocarbons (PCA, abbreviated as PCA, measured by the British Petroleum institute method IP 346) in oils such as rubber oils is less than 3%, and that the benzo (a) pyrene content is not more than 1mg/kg, the benzo (a) anthracene, the aromatic hydrocarbon, and the aromatic hydrocarbon are present in the oils,
The total content of eight specific Polycyclic Aromatic Hydrocarbons (PAHs) including benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, benzo (e) pyrene and dibenzo (a, h) anthracene is not more than 10mg/kg, the aromatic rubber oil meeting the requirements of the environmental protection indexes is called as environment-friendly aromatic rubber oil, and the environment-friendly aromatic rubber oil also gradually becomes the research and development direction.
At present, mainly a solvent extraction method is adopted to prepare rubber oil, for example, patent document CN101684185A discloses a production method of high aromatic hydrocarbon environment-friendly rubber oil, in which light hydrocarbon is mixed with raw oil, then the mixture enters an extraction tower, and is extracted and refined with methyl pyrrolidone, phenol or furfural solvent in the extraction tower, and the refined liquid is recovered by the solvent to obtain the environment-friendly rubber oil; CN103725317A discloses a method for producing aromatic rubber filling oil, which comprises mixing raw oil with light alkane of C6-C12, carrying out solvent extraction, optionally, recycling a part of the extracted oil to an extraction tower to dissolve a dewaxing assistant in the raffinate oil obtained in the step, and then carrying out solvent dewaxing, wherein the dewaxing assistant 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 base distillate oil and deasphalted oil as raw materials to carry out two-stage solvent extraction to prepare the rubber oil (secondary extract oil); WO9844075 discloses a method for re-extracting and treating aromatic oil by using a selective solvent, which can prepare environment-friendly aromatic oil by using extract oil in a lubricating oil solvent refining process as a raw material and using dimethyl sulfoxide (DMSO) as a solvent.
By adopting the solvent extraction mode, the defects of high viscosity of extract oil, blockage of extraction tower filler, low product yield (most of the extract oil does not exceed 40 wt%) and the like generally exist, so the practical application is limited. Therefore, optimizing the preparation method of rubber oil and improving the comprehensive properties such as environmental protection and the like and the yield thereof are important subjects faced by those 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: mixing raw oil with a composite solvent, and then carrying out crystallization and dewaxing treatment to respectively obtain wax crystals and dewaxed oil; carrying out desolventizing treatment after the wax is crystallized to form a liquid state, so as to obtain rubber oil; wherein the composite solvent comprises furfural and a ketone solvent.
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, the rubber oil can be co-produced, and the yield of the rubber oil is higher. The inventor considers that the furfural is soluble to aromatic hydrocarbon, can realize concentration and separation of aromatic hydrocarbon components in raw oil, and simultaneously introduces a ketone solvent (almost insoluble to oil/hydrocarbon components) which are cooperated to improve the selectivity in the crystallization dewaxing treatment process, so that the yield of refined oil (namely the rubber oil) is greatly improved.
The present invention can employ ketone solvents conventional in the art, such as lower ketones having a carbon number not higher than 4 or higher ketones having a carbon number greater than 4 or a mixture of the two, etc., and in some preferred embodiments, such ketone solvents may generally comprise butanone. The freezing point of the furfural is-36.5 ℃, the condensed ring aromatic hydrocarbon can be dissolved, and after the condensed ring aromatic hydrocarbon is dissolved, the good fluidity (similar to the fluidity at room temperature) can be still maintained under the condition of-30 ℃, and the freezing point of the butanone is-86 ℃, so that the composite solvent formed by the two components can still maintain very good fluidity and is completely mutually soluble under the condition of crystallization temperature (such as-30 ℃ to-45 ℃ or-30 ℃ to-35 ℃ below), and the dewaxing treatment efficiency can be further 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 the quality and yield of rubber oil.
Through further research, the mass ratio of the composite solvent to the raw oil can be 2-10:1, and further can be 2-9:1, 2-8:1, 2-7:1, 2-6:1, 2-5:1 or 2-4: 1.
In the present invention, the feedstock may be a furfural extract oil (which may be generally referred to as a naphthenic aromatic oil) of naphthenic Distillate (DAE), and further may be a furfural extract oil of vacuum distillate of naphthenic distillate having a distillation range of 300-. Specifically, the raw oil may be furfural extract oil obtained by subjecting vacuum distillate of naphthenic distillate to hydrogenation deacidification, solvent deacidification-furfural refining, and the like, which are conventional processes in the art, and may be at least one of furfural extract oil with a reduced trilinear structure and furfural extract oil with a reduced quadrilinear structure.
In the aspect of rubber oil production, because the polycyclic aromatic hydrocarbons and other aromatic hydrocarbons in the DAE raw material are in symbiotic relationship, if the conventional secondary extraction process is adopted to produce or prepare the environment-friendly rubber oil, an extraction solvent such as furfural is generally required to be utilized, and the effects that the polycyclic aromatic hydrocarbons are lower and other non-polycyclic aromatic hydrocarbon components are kept as much as possible are hardly obtained by the conventional adjusting means of processes such as furfural refining and the like, and the yield of refined oil (rubber oil product) is usually not more than 50 wt%.
Specifically, the feedstock oil and the complex solvent may be mixed and then crystallized at a reduced temperature, and in one embodiment of the present invention, the crystallization temperature may be in the range of-40 ℃ to-30 ℃ and may be in the range of-35 ℃ to-30 ℃ in the crystallization dewaxing treatment. In general, most of naphthenic aromatic oil (such as furfural extraction oil with three lines reduced/four lines reduced) components are in a solidification state under the condition of-40 ℃ to-30 ℃, and the crystallization treatment is carried out under the low temperature condition, so that the wax components are precipitated and crystallized, and the yield and the quality of the rubber oil are improved.
Further, in the above-mentioned crystallization dewaxing treatment, the time for crystallization is generally not less than 30min, for example, 30min to 240min, preferably 60min to 180min, and in the specific implementation, the cooling of the mixed system formed by mixing the feedstock oil and the complex solvent at the crystallization temperature (e.g., the above-mentioned-40 ℃ to-30 ℃ or-35 ℃ to-30 ℃) is not less than 30 min. 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 settling can be continued at the crystallization temperature for a period of time, such as 30 +/-10 min, so that separation of wax crystallization and dewaxed oil (such as subsequent filtration and other treatment) is facilitated.
In a preferred embodiment of the invention, the composite solvent can be added into the raw oil for multiple times, after each addition, the temperature reduction treatment is carried out on the system containing the composite solvent and the raw oil, and after all the composite solvent is added, the obtained mixed system is cooled to-40 ℃ to-30 ℃ for crystallization, in the mode, the composite solvent is adopted to carry out gradual dilution and temperature reduction (or called segmented dilution and temperature reduction) on the raw oil, so that the quality and the yield of the rubber oil can be further improved; wherein, the rate of the temperature reduction can be 25 +/-5 ℃/h.
Further, the composite solvent can be added into the raw oil for 2 to 6 times.
In a preferred embodiment, the mass ratio (or dilution ratio) of the composite solvent to the raw oil added each time is greater than 0.5: 1 may be, for example, 0.5 to 1.5, further 0.5 to 1.0 or 0.75 to 1.0.
In specific implementation, after the composite solvent is added each time, stirring can be carried out to accelerate the mixing of the composite solvent and the raw oil system, then the obtained system can be allowed to stand (settle) for about 20-40min, and then cooling treatment is carried out, which is beneficial to improving the yield and quality of the rubber oil.
In an embodiment of the present invention, in the process of diluting and cooling the raw oil step by using the composite solvent, the raw oil may be diluted at the same temperature by using the composite solvent, that is, the temperature of the composite solvent to be added at each time is the same as the temperature of the raw oil system to be mixed with the composite solvent to be added, specifically, the composite solvent may be divided into n portions and added to the raw oil n times; wherein the temperature of the raw oil is made to be the same as that of the part 1 complex solvent, after the part 1 complex solvent is added to the raw oil, cooling the obtained 1 st system to 1 st dilution temperature, controlling the temperature of the 2 nd part of composite solvent to be equal to the 1 st dilution temperature, adding the 2 nd part of composite solvent into the 1 st system, cooling the obtained system 2, reducing the temperature to … … to obtain a dilution temperature of the system 2, controlling the temperature of the composite solvent of the nth part to be equal to the dilution temperature of the nth-1 part, adding the composite solvent of the nth part into the nth-1 system, cooling the obtained nth system (namely a mixed system formed by adding all the composite solvent into the raw oil) to the crystallization temperature of (-40 ℃ to-30 ℃ or-35 ℃ to-30 ℃), and then carrying out cold insulation and crystallization; where n is 2 to 6, the composite solvent may be divided into n portions on average (i.e., the amount of the composite solvent is equal to each 1 portion).
Generally, the gradual dilution and temperature reduction (namely the completion of feeding) of the compound solvent to the raw oil can be completed in the interval of 60 ℃ to-25 ℃, that is, the temperature of the raw oil and the part 1 compound solvent can be 60 ℃, and the temperature of the part n compound solvent can be-25 ℃.
Of course, the temperature of the raw oil of the present invention is not limited to 60 ℃, and may be generally 40 to 70 ℃, for example, 50 to 60 ℃ or 45 to 60 ℃, which can prevent the separation of components such as wax in the raw oil and the like from affecting the mixing of the raw oil and the complex solvent.
Further, after the crystallization dewaxing treatment, the obtained mixed feed liquid in which the wax crystals are suspended can be filtered to obtain the wax crystals and the dewaxed oil; wherein the filtering temperature can be-35 ℃ to-25 ℃; the filtration may specifically be vacuum filtration.
The wax crystal is mainly in a cerate (non-liquid state) form at the crystallization-filtration temperature, and is generally in a liquid state when placed at room temperature, and generally contains part of composite solvent due to entrainment, and the final environment-friendly rubber oil product is obtained after the composite solvent is subjected to desolventizing treatment. The complex solvent in wax crystallization can be removed by a distillation method according to the boiling point of butanone (79.6 ℃) and the boiling point of furfural (161.4 ℃), and specifically, in an embodiment of the invention, the solvent removal treatment process can comprise the following steps: carrying out atmospheric distillation or reduced pressure distillation on the liquid formed by wax crystallization, and removing the solvent in the liquid to obtain rubber oil;
the invention can adopt the conventional method in the field to carry out the atmospheric distillation or the reduced pressure distillation, concretely, in the reduced pressure distillation process, the residual pressure of the system can be about 100mmHg when the pressure is reduced, when the temperature of the distillation outlet of the pressurization system is equal to the atmospheric temperature of more than 161 ℃, and the liquid phase temperature reaches 190-200 ℃, the solvent including butanone and furfural is considered to be completely removed, then the liquid phase after the solvent is removed is cooled to 80-100 ℃, the vacuum is broken and the air is released, and the liquid phase product is taken out to be the environment-friendly rubber oil.
In the present invention, the dewaxing treatment can be performed by using a conventional continuous/batch dewaxing industrial apparatus or experimental apparatus in the art, for example, a conventional acetone-benzol dewaxing industrial apparatus or experimental apparatus composed of a crystallization system, a freezing system, a vacuum filtration system and a solvent recovery system can be used, and during the specific operation, the treatment such as feeding according to the conventional acetone-benzol dewaxing process can be performed, which is not described again.
The implementation of the invention has at least the following beneficial effects:
according to the crude oil dewaxing method disclosed by the invention, the raw oil is subjected to crystallization dewaxing treatment by adopting the composite solvent formed by the furfural and the ketone solvent, so that the wax component in the raw oil can be effectively removed, the influence of the wax on the subsequent production of the raw oil is solved, the environment-friendly rubber oil product is co-produced, the yield of the environment-friendly rubber oil product can be improved, and the method has important practical significance.
Detailed Description
In order to make 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 below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
in this embodiment, a conventional continuous dewaxing system having a structure of solvent dilution and distribution, raw material/solvent mixing, solvent (diluent) cooling (jacket type), mixed material cooling crystallization (jacket type), and the like is used to perform dewaxing processing on raw oil, and in the dewaxing process, the related temperature reduction/temperature rise/heat preservation may be controlled by a system temperature rise/temperature reduction program, specifically, cooling and temperature reduction may be performed by a refrigerant forced circulation method, and details are not repeated.
In this embodiment, the composite solvent is divided into n portions, and the n portions are added to the raw oil in n times, and the process is specifically as follows:
feeding the raw oil into a crystallizing tank, and keeping the temperature to 45-60 ℃; heating the composite solvent in a cooling tank (an electric stirring paddle with a cooling jacket, a lower discharge hole and an upper feed hole) to the heat preservation temperature of the raw oil, adding a part of the composite solvent (namely the 1 st part of the composite solvent) into a crystallizing tank, mixing the composite solvent with the raw oil under the stirring condition, stopping stirring, standing for 30min, starting stirring, cooling and reducing the temperature to the 1 st dilution temperature; cooling the rest of the composite solvent in the cooling tank to 0 ℃, adding a part (2 nd part of the composite solvent) into a crystallizing tank, mixing the composite solvent with the 1 st system under the condition of stirring, stopping stirring, standing for 30min, starting stirring, cooling, reducing the temperature of the obtained 2 nd system to the 2 nd dilution temperature … …, cooling the rest of the composite solvent in the cooling tank to the n-1 th dilution temperature, adding the (n th part of the composite solvent) into the crystallizing tank, mixing the composite solvent with the n-1 th system under the condition of stirring, stopping stirring, standing for 30min, starting stirring, cooling, reducing the temperature of the obtained n th system (namely the mixed system formed after all the composite solvent is added into the raw oil) to the crystallization temperature of (-40 ℃ to-30 ℃ or-35 ℃ to-30 ℃), then cooling and crystallizing; wherein n is 2-6, and the cooling rate in the cooling process is 25 ℃/h; equally dividing the composite solvent into n parts (namely, the quantity of the composite solvent in each 1 part is equal);
after the cold insulation crystallization is finished, obtaining mixed feed liquid of suspended wax crystals; introducing the mixed feed liquid into a freezing box through a cold insulation pipeline, and carrying out vacuum filtration on the mixed feed liquid to obtain filtrate (namely dewaxed oil) and wax crystals; wherein the temperature of the freezing box is controlled to be vacuum filtration temperature (namely-35 ℃ to-25 ℃), and before filtration, the used filter paper, Buchner funnel, filtration bottle and the like are all kept at the constant temperature/precooled for 1h in the freezing box at the temperature of-35 ℃ to-25 ℃;
and (2) carrying out reduced pressure distillation on wax crystals to remove the entrained composite solvent, wherein the residual pressure of a system is 100mmHg during reduced pressure, when the temperature of a distillation outlet is converted to be equivalent to the normal pressure temperature of more than 161 ℃, and the liquid phase temperature reaches 200 ℃, the solvent including butanone and furfural is considered to be completely removed, then the liquid phase after solvent removal is cooled to 90 ℃, vacuum breaking and emptying are carried out, and the liquid phase product is taken out to be the environment-friendly rubber oil.
Dewaxing was carried out according to the procedure described above on three aromatic extract oils A, B, C, A, B, C having the properties shown in table 1, a dewaxing test on a was designated as test 1a, a dewaxing test on B was designated as test 1B, and a dewaxing test on C was designated as test 1C;
in tests 1a, 1b and 1c, the test conditions of the composition of the complex solvent during dewaxing, the mass ratio of the complex solvent to the feedstock oil (solvent ratio in table 1), the mass ratio of the amount of the complex solvent added to each 1 part to the feedstock oil (dilution ratio in table 1), the number of dilution stages (i.e., the value of n), the cooling temperature (i.e., crystallization temperature), the cooling time, the vacuum filtration temperature, the vacuum filtration time, the yield of the environmentally-friendly rubber oil, and the like are shown in table 2, and the physical properties of the obtained environmentally-friendly rubber oil are shown in table 3.
TABLE 1 Properties of the stock oils
TABLE 2 test conditions
TABLE 3 rubber oil Properties
Claims (10)
1. A method for dewaxing a feedstock, comprising: mixing raw oil with a composite solvent, and then carrying out crystallization and dewaxing treatment to respectively obtain wax crystals and dewaxed oil; carrying out desolventizing treatment after the wax is crystallized to form a liquid state, so as to obtain rubber oil; wherein the composite solvent comprises furfural and a ketone solvent.
2. A dewaxing method according to claim 1, wherein said ketone solvent comprises butanone.
3. A dewaxing method according to claim 1 or 2, wherein the volume fraction of furfural and the volume fraction of ketone solvent in said composite solvent are 89-99% and 1-11%.
4. The dewaxing method according to claim 1, wherein the mass ratio of the composite solvent to the raw oil is 2-10: 1;
preferably, the mass ratio of the composite solvent to the raw oil is 2-4: 1.
5. A dewaxing method according to claim 1 or 4, wherein the feed oil comprises a furfural extract of naphthenic distillate, and the distillation range of the naphthenic distillate is 300-520 ℃.
6. The dewaxing method of claim 1, wherein the temperature of crystallization during the crystallization dewaxing treatment is in the range of-40 ℃ to-30 ℃;
preferably, the crystallization time is not less than 30 min.
7. A dewaxing method according to claim 1 or 6, wherein the complex solvent is added to the stock oil in a plurality of times, after each addition, the temperature of the system containing the complex solvent and the stock oil is reduced, and after all the complex solvent is added, the obtained mixed system is cooled to-40 ℃ to-30 ℃ for crystallization;
preferably, the cooling rate is 25 +/-5 ℃/h;
preferably, the composite solvent is added into the raw oil for 2 to 6 times.
8. A dewaxing method according to claim 7, wherein the mass ratio of the composite solvent to the raw oil added each time is more than 0.5: 1.
9. a dewaxing method according to claim 1 or 6, wherein after said crystallizing dewaxing treatment, the obtained mixed liquor is filtered to obtain wax crystals and dewaxed oil; wherein the filtering temperature is-35 ℃ to-25 ℃;
preferably, the filtration is vacuum filtration.
10. The dewaxing method of claim 1, wherein the desolventizing step comprises: and (3) carrying out atmospheric distillation or reduced pressure distillation on the liquid formed by wax crystallization, and removing the solvent to obtain the rubber oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011190492.7A CN114437760B (en) | 2020-10-30 | 2020-10-30 | Dewaxing method for raw oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011190492.7A CN114437760B (en) | 2020-10-30 | 2020-10-30 | Dewaxing method for raw oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114437760A true CN114437760A (en) | 2022-05-06 |
| CN114437760B CN114437760B (en) | 2023-12-22 |
Family
ID=81357717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011190492.7A Active CN114437760B (en) | 2020-10-30 | 2020-10-30 | Dewaxing method for raw oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114437760B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2020
- 2020-10-30 CN CN202011190492.7A patent/CN114437760B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 李淑培: "《石油加工工艺学 下册》", 31 January 1992, 中国石化出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114437760B (en) | 2023-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102676212B (en) | Raw oil optimization method for improving environment-friendly rubber filling oil aromatic hydrocarbon content and equipment | |
| EP2834331A2 (en) | Process to prepare residual base oil | |
| CN112574785A (en) | Deoiling method and application of Fischer-Tropsch synthetic wax | |
| CN103589453A (en) | Preparation method of aromatic rubber oil | |
| CA1050914A (en) | Production of lubricating oils blending stocks | |
| CN114437760A (en) | Raw oil dewaxing method | |
| US8864981B2 (en) | Feed mixtures for extraction process to produce rubber processing oil | |
| JPH08508761A (en) | Dewaxing of lubricating oil using low temperature solvent membrane separation from dewaxed oil | |
| CN102676214B (en) | Solvent refining method and equipment for producing environmental-protection rubber filling oil | |
| US4081352A (en) | Combination extraction-dewaxing of waxy petroleum oils | |
| CN109705895B (en) | Process for producing lube base oil and naphthenic base oil | |
| CN103725317B (en) | A kind of production method of aromatic hydrocarbon rubber extender oil | |
| CN102191082B (en) | Preparation method of aromatic hydrocarbon rubber oil | |
| US7186876B2 (en) | Process to prepare a process oil | |
| CN103725318A (en) | Production method of filling distillate aromatic extract | |
| CN109694747B (en) | Keto-benzene dewaxing process for low-wax-content raw material | |
| CN109694745B (en) | Method for recovering dewaxing solvent for heavy lubricant oil feedstock and method for dewaxing heavy lubricant oil feedstock | |
| CN115386396B (en) | Refined Fischer-Tropsch wax and preparation method and preparation system thereof | |
| CN103725319A (en) | Production method of filling distillate aromatic extract | |
| CN102676213B (en) | Solvent refining method and solvent refining equipment for producing environment-friendly rubber filling oil | |
| US2129616A (en) | Manufacture of improved lubricating oils | |
| Starkova et al. | Increasing the efficiency of dewaxing in the deoiling stage | |
| JPH0653877B2 (en) | Dewaxing method of lubricating oil material | |
| USRE18676E (en) | of fobt wobth | |
| JPS6144992A (en) | Production of crude raw pitch for carbon fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |