CN109694729B - Preparation method of white oil - Google Patents
Preparation method of white oil Download PDFInfo
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- CN109694729B CN109694729B CN201711001314.3A CN201711001314A CN109694729B CN 109694729 B CN109694729 B CN 109694729B CN 201711001314 A CN201711001314 A CN 201711001314A CN 109694729 B CN109694729 B CN 109694729B
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
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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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
Abstract
The invention relates to the technical field of ketone-benzene dewaxing, in particular to a preparation method of white oil. The preparation method comprises the following steps: 1) dewaxing: mixing a low-wax raw material with a first ketobenzene dewaxing solvent, and filtering and separating to obtain a dewaxing filtrate and an oil-containing wax liquid; 2) first-stage deoiling: mixing the oil-containing wax liquid with a second diketone benzene dewaxing solvent, and then dividing the mixture into a first oil-containing wax liquid and a second oil-containing wax liquid; 3) second-stage deoiling: mixing the first-stage deoiled wax liquid, the second oil-containing wax liquid and a third ketone-benzene dewaxing solvent, dividing the mixture into a third oil-containing wax liquid and a fourth oil-containing wax liquid, and filtering and separating the third oil-containing wax liquid to obtain a second-stage deoiled filtrate and a second-stage oil-containing wax liquid; 4) and (4) clay refining. The preparation method ensures the low-temperature fluidity of the product by the acetone-benzol dewaxing of the low-wax raw material, can process the low-wax raw material, has stable process operation and obtains the dewaxed oil with qualified solidifying point, ensures the stability, impurities and color of the product by the clay refining, and ensures the odor of the product by increasing the consumption of stripping steam.
Description
Technical Field
The invention relates to the technical field of white oil, in particular to a preparation method of white oil.
Background
The white oil is a special mineral oil product obtained by removing impurities such as aromatic hydrocarbon, sulfur, nitrogen and the like through ultra-deep refining, the components of the white oil are generally cycloparaffin and alkane with the relative molecular mass of 300-400, the white oil belongs to lubricating oil fractions, and the white oil is colorless, tasteless and odorless, has chemical inertness, excellent light and heat stability and wide application. White oil is regarded as a product with higher added value and is being valued by the petrochemical industry in China.
The white oil classification in China is different from foreign countries, and the foreign countries are generally divided into two types: one is technical grade white oil; the other is food and medicine white oil. The domestic classification is three grades, namely industrial grade, cosmetic grade and food and medicine grade. The main property indexes are as follows: viscosity, chromaticity, easy charring, ultraviolet absorption, freezing point, etc. The industrial white oil is mainly used for chemical fiber, aluminum processing and rubber plasticization, and is also used for lubricating textile machinery and precision instruments and used as oil for sealing compressors; the special white oil for food machinery is used for lubricating food processing machinery and equipment which are not in direct contact with food, and comprises the lubrication of food industrial processing equipment for grain and oil processing, fruit and vegetable processing, dairy product processing and the like; the cosmetic white oil is used as industrial raw material for cosmetics, and can be used for preparing hair cream, hair oil, lipstick, skin care cream, etc. The white oil has different grades and specifications, and the price difference is large and is often several times or even dozens of times. Generally, white oil products with higher viscosity are more expensive and more profitable.
The domestic white oil production process mainly comprises fuming sulfuric acid sulfonation, sulfur trioxide sulfonation and hydrofining. The white oil produced by the fuming sulfuric acid sulfonation and sulfur trioxide sulfonation processes accounts for a large proportion, and accounts for about more than 2/3 of the total yield of the white oil. The white oil hydrofining method has been studied and applied for more than 20 years, but the development is slow, the white oil produced by the hydrogenation method has a low percentage, and the white oil is about 4/5 or more in developed countries.
The prior white oil processing technology is a patent CN101429457 (a method for producing white oil by distillate oil hydrogenation) applied by Shikoyao, a hydrocarbon oil feed is subjected to a hydrotreating reaction unit, a dewaxing reaction unit and a hydrofining unit to obtain white oil product oil, the method needs three-section high-pressure hydrogenation, the equipment investment is large, a catalyst contains noble metals, and the catalyst operation cost is high.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a process for the preparation of a white oil. The preparation method comprises the following steps: 1) dewaxing: mixing a low-wax raw material with a first ketobenzene dewaxing solvent, and then filtering and separating to obtain a dewaxing filtrate and an oil-containing wax liquid; 2) first-stage deoiling: mixing the oil-containing wax liquid obtained in the step 1) with a second benzol dewaxing solvent, and then dividing the mixture into a first oil-containing wax liquid and a second oil-containing wax liquid, wherein the mass ratio of the first oil-containing wax liquid to the second oil-containing wax liquid is 50-70: 30-50, filtering and separating the first oil-containing wax liquid to obtain a first-stage deoiled filtrate and a first-stage deoiled wax liquid; 3) second-stage deoiling: mixing the first-stage deoiled wax liquid, the second oil-containing wax liquid and a third ketone-benzene dewaxing solvent, and then dividing the mixture into a third oil-containing wax liquid and a fourth oil-containing wax liquid, wherein the mass ratio of the third oil-containing wax liquid to the fourth oil-containing wax liquid is 40-60: 40-60, filtering and separating the third oil-containing wax liquid to obtain a second-stage deoiling filtrate and a second-stage oil-containing wax liquid; 4) clay refining: and (3) adsorbing the dewaxing filtrate obtained in the step 1) by using clay to obtain the white oil. The preparation method ensures the low-temperature fluidity of the product by the acetone-benzol dewaxing of the low-wax raw material, can process the low-wax raw material, has stable process operation and obtains the dewaxed oil with qualified solidifying point, ensures the stability, impurities and color of the product by the clay refining, and ensures the odor of the product by increasing the consumption of stripping steam.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing white oil, comprising the steps of:
1) dewaxing: mixing a low-wax raw material with a first ketobenzene dewaxing solvent, and then filtering and separating to obtain a dewaxing filtrate and an oil-containing wax liquid;
2) first-stage deoiling: mixing the oil-containing wax liquid obtained in the step 1) with a second benzol dewaxing solvent, and then dividing the mixture into a first oil-containing wax liquid and a second oil-containing wax liquid, wherein the mass ratio of the first oil-containing wax liquid to the second oil-containing wax liquid is 50-70: 30-50, such as 50: 50-60: 40 or 60: 40-70: 30, filtering and separating the first oil-containing wax liquid to obtain a first-stage deoiling filtrate and a first-stage deoiling wax liquid;
in the process of producing the low-wax raw material, the wax content in the low-wax raw material is less than or equal to 12 wt%, such as 5-7 wt%, 7-9 wt% or 9-12 wt%, after the low-wax raw material is filtered by a dewaxing filter, the wax liquid is less, the oil-containing wax liquid overflows from a partial first-section deoiling filter, namely the partial first-section deoiling filter stops vacuum suction, and the material originally entering the oil recovery under the wax is overflowed and then is subjected to second-section deoiling filtration;
3) second-stage deoiling: mixing the first-stage deoiled wax liquid, the second oil-containing wax liquid and a third ketone-benzene dewaxing solvent, and then dividing the mixture into a third oil-containing wax liquid and a fourth oil-containing wax liquid, wherein the mass ratio of the third oil-containing wax liquid to the fourth oil-containing wax liquid is 40-60: 40-60, such as 40: 60-50: 50 or 50: 50-60: 40, filtering and separating the third oil-containing wax liquid to obtain a second-stage deoiling filtrate and a second-stage oil-containing wax liquid;
by adopting the ketobenzene dewaxing process of the low-wax-content raw material, the material balance of wax recovery can be ensured, and further the heat balance of the wax recovery is ensured;
4) clay refining: and (3) adsorbing the dewaxing filtrate obtained in the step 1) by using clay to obtain the white oil.
Preferably, the distillation range of the low-wax raw material is 250-360 ℃, the wax content is less than or equal to 12 wt%, such as 5-7 wt%, 7-9 wt% or 9-12 wt%, the flash point is 150-170 ℃, and the freezing point is 6-14 ℃.
Preferably, the first, second and third ketone-benzene dewaxing solvents are a mixture of methyl ethyl ketone and toluene, and the content of methyl ethyl ketone is 30 to 80 wt%, such as 30 to 60 wt% or 60 to 80 wt%.
Preferably, step 1) further comprises one or more of the following features:
1) the feeding temperature of the low-wax raw material is-25-20 ℃, such as-25-0 ℃ or 0-20 ℃;
2) the mass ratio of the first ketone-benzene dewaxing solvent to the low-wax raw material is 2-9.5, such as 2-6 or 6-9.5;
3) the first ketone-benzene dewaxing solvent is diluted for three times and then cold washed, wherein the first time ratio is 0.5-2.0, such as 0.5-1 or 1-2.0, the second time ratio is 0.5-2.5, such as 0.5-1.5 or 1.5-2.5, the third time ratio is 0.5-3.0, such as 0.5-2 or 2-3.0, the cold washing ratio is 0.5-2.0, such as 0.5-1.5 or 1.5-2.0, and the cold washing temperature is-20 to-10 ℃, such as-20 to-15 ℃ or-15 to-10 ℃.
The first ratio is the mass ratio of the first-time added ketobenzene dewaxing solvent to the low-wax raw material, the second ratio is the mass ratio of the second-time added ketobenzene dewaxing solvent to the low-wax raw material, and the third ratio is the mass ratio of the third-time added ketobenzene dewaxing solvent to the low-wax raw material; the cold wash ratio is the mass ratio of the ketone-benzene dewaxing solvent used for cold washing to the low wax feed.
Preferably, step 2) further comprises one or more of the following features:
1) the feeding temperature of the oil-containing wax liquid obtained in the step 1) is 0-20 ℃, such as 0-10 ℃ or 10-20 ℃;
2) the mass ratio of the second ketone benzene dewaxing solvent to the oily wax liquid obtained in the step 1) is 1-5, such as 1-1.9 or 1.9-5;
3) diluting the second benzene dewaxing solvent and then cold washing, wherein the dilution ratio of the first-stage deoiling is 0.5-3.0, such as 0.5-1 or 1-3.0, and the cold washing ratio of the first-stage deoiling is 0.5-2.0, such as 0.5-0.9 or 0.9-2.0; preferably, the cold washing temperature of the first-stage deoiling is 0-20 ℃, such as 0-10 ℃ or 10-20 ℃.
The dilution ratio refers to the mass ratio of the second benzol dewaxing solvent added during the first-stage deoiling to the oil-containing wax liquid obtained in the step 1); the cold washing ratio is the mass ratio of the second ketone benzene dewaxing solvent for cold washing to the oil-containing wax liquid obtained in the step 1).
Preferably, step 3) further comprises one or more of the following features:
1) the feeding temperature of the first-stage deoiling wax liquid is 0-20 ℃, such as 0-10 ℃ or 10-20 ℃;
2) the mass ratio of the total mass of the first-stage deoiled wax liquid and the second oil-containing wax liquid to the third ketone-benzene dewaxing solvent is 1: 1-5, such as 1: 1-2.6 or 1: 2.6-5;
3) the third ketone benzene dewaxing solvent is diluted and then cold washed, the dilution ratio of the second-stage deoiling is 0.5-3.0, such as 0.5-1.6 or 1.6-3.0, and the cold washing ratio of the second-stage deoiling is 0.5-2.0, such as 0.5-1.0 or 1.0-2.0; preferably, the cold washing temperature of the two-stage deoiling is 0-20 ℃, such as 0-10 ℃ or 10-20 ℃.
The dilution ratio is the ratio of the mass of the third ketone-benzene dewaxing solvent added during the second-stage deoiling to the total mass of the first-stage deoiled wax liquid and the second oil-containing wax liquid; the cold wash ratio is the ratio of the mass of the third ketone benzene dewaxing solvent used for cold wash to the total mass of the first-stage deoiled wax liquid and the second oil-containing wax liquid.
Preferably, one or more of the following features are also included:
1) recovering the dewaxing filtrate obtained in the step 1) to obtain dewaxed oil and a ketone-benzene dewaxing recovered solvent;
2) recovering the first-stage deoiled filtrate obtained in the step 2) through wax oil to obtain wax oil and a ketone-benzene dewaxing recovery solvent;
3) mixing the second-stage oil-containing wax liquid obtained in the step 3) with the fourth oil-containing wax liquid, and recovering wax to obtain refined wax and a ketone-benzene dewaxing recovery solvent.
More preferably, in the characteristic 1), the freezing point of the dewaxed oil is-24 to-3 ℃, and the content of the ketone-benzene dewaxing solvent in the dewaxed oil is 0 to 100 mg/kg.
More preferably, in the characteristic 3), the material obtained after the fourth oily wax liquid overflows through the deoiling filter is mixed with the second-stage oily wax liquid obtained in the step 3), and then the refined wax and the wax recovery solvent are obtained through wax recovery. The fourth oily wax liquid overflows through the deoiling filter, namely the deoiling filter stops vacuum suction, and the filtrate which is originally sucked in the vacuum is overflowed and then is removed to recover the wax.
More preferably, one or more selected from the group consisting of the recovered solvent by ketone benzene dewaxing in characteristic 1), the recovered solvent by ketone benzene dewaxing in characteristic 2), and the recovered solvent by ketone benzene dewaxing in characteristic 3) is returned to step 1) for use.
More preferably, the mass ratio of the fresh ketone-benzene dewaxing solvent to the recovered ketone-benzene dewaxing solvent used in the step 1) is 1-5: 1, as 1-3: 1 or 3-5: 1.
preferably, in step 3), the first-stage deoiled wax liquid, the ketone-benzene dewaxing solvent and the material after the second oil-containing wax liquid overflows through the deoiling filter are mixed and then divided into a third oil-containing wax liquid and a fourth oil-containing wax liquid. The overflow of the deoiling filter means that the deoiling filter stops vacuum suction, and the material originally entering the undersize oil recovery is overflowed and then goes to the second-stage deoiling filtration.
Preferably, the secondary de-oiling filtrate obtained in step 3) is returned to step 2).
Preferably, step 4) further comprises one or more of the following features:
1) the dosage of the argil is 0.5-5% of the mass of the dewaxing filtrate obtained in the step 1), such as 0.5-3.5% or 3.5-5%;
2) the reaction time is 30-90 min, such as 30-60 min or 60-90 min;
3) the feeding temperature is 80-120 ℃, such as 80-100 ℃ or 100-120 ℃;
4) the temperature of the white oil outlet device is 30-60 ℃, such as 30-45 ℃ or 45-60 ℃.
The preparation method comprises the following steps: 1) dewaxing: mixing a low-wax raw material with a first ketobenzene dewaxing solvent, and then filtering and separating to obtain a dewaxing filtrate and an oil-containing wax liquid; 2) first-stage deoiling: mixing the oil-containing wax liquid obtained in the step 1) with a second benzol dewaxing solvent, and then dividing the mixture into a first oil-containing wax liquid and a second oil-containing wax liquid, wherein the mass ratio of the first oil-containing wax liquid to the second oil-containing wax liquid is 50-70: 30-50, filtering and separating the first oil-containing wax liquid to obtain a first-stage deoiled filtrate and a first-stage deoiled wax liquid; 3) second-stage deoiling: mixing the first-stage deoiled wax liquid, the second oil-containing wax liquid and a third ketone-benzene dewaxing solvent, and then dividing the mixture into a third oil-containing wax liquid and a fourth oil-containing wax liquid, wherein the mass ratio of the third oil-containing wax liquid to the fourth oil-containing wax liquid is 40-60: 40-60, filtering and separating the third oil-containing wax liquid to obtain a second-stage deoiling filtrate and a second-stage oil-containing wax liquid; 4) clay refining: and (3) adsorbing the dewaxing filtrate obtained in the step 1) by using clay to obtain the white oil. The preparation method ensures the low-temperature fluidity of the product by the acetone-benzol dewaxing of the low-wax raw material, can process the low-wax raw material, has stable process operation and obtains the dewaxed oil with qualified solidifying point, ensures the stability, impurities and color of the product by the clay refining, and ensures the odor of the product by increasing the consumption of stripping steam.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The distillation range of the low-wax raw material is 250-360 ℃, the wax content is less than or equal to 12 wt%, the flash point is 150-170 ℃, the freezing point is 6-14 ℃, and specific typical properties are shown in the following table:
| index (I) | Low wax feed |
| Water (mixed)% (mass fraction) | 0.03 |
| Kinematic viscosity (50 ℃ C.), mm2/s | 7.356 |
| Kinematic viscosity (100 ℃ C.), mm2/s | 2.200 |
| Initial cut point, DEG C | 304.5 |
| 50% recovery temperature, deg.C | 333.5 |
| End point of distillation,. degree.C | 363.5 |
| Wax content,% (mass fraction) | 10.74 |
| Freezing point, deg.C | 8 |
| Chroma, number (Saishi color comparison) | +26 |
| Flash point (closed mouth), deg.C | 161 |
| Density (20 ℃), kg/m3 | 827.9 |
| Sulfur content% | 0.0002 |
Example 1
A ketone-benzene dewaxing process for low wax content raw materials comprises the following steps:
1) dewaxing: diluting a low-wax raw material by using a first ketone-benzene dewaxing solvent for three times, then carrying out cold washing, and filtering and separating to obtain a dewaxing filtrate and an oil-containing wax liquid; the wax content of the low-wax raw material is 9 wt%, and the feeding temperature is-25 ℃; the primary ratio is 1; the secondary ratio is 1.5; the third ratio is 2; the cold washing ratio is 1.5, and the cold washing temperature is-20 ℃; the distillation range of the low-wax raw material is 304-364 ℃, the wax content is 9 wt%, the flash point is 161 ℃, and the freezing point is 8 ℃;
2) first-stage deoiling: diluting the oil-containing wax liquid obtained in the step 1) by using a second benzene dewaxing solvent, and then performing cold washing to obtain a mixture which is divided into a first oil-containing wax liquid and a second oil-containing wax liquid; the mass ratio of the first oil-containing wax liquid to the second oil-containing wax liquid is 50: 50, filtering and separating the first oil-containing wax liquid to obtain a first-stage deoiling filtrate and a first-stage deoiling wax liquid; the feeding temperature of the oil-containing wax liquid obtained in the step 1) is 0 ℃; the dilution ratio of the first-stage deoiling is 0.5; the cold washing ratio of the first-stage deoiling is 2.0; the cold washing temperature of the first-stage deoiling is 0 ℃; recovering the obtained first-stage deoiled filtrate by using wax oil to obtain wax oil and a ketone-benzene dewaxing recovery solvent, wherein the yield of the wax oil is 7.8%;
3) second-stage deoiling: the third ketone-benzene dewaxing solvent firstly dilutes the material of the first-stage deoiled wax liquid and the second oily wax liquid after overflowing through the deoiling filter, and then carries out cold washing, and the obtained mixture is divided into a third oily wax liquid and a fourth oily wax liquid; the mass ratio of the third oil-containing wax liquid to the fourth oil-containing wax liquid is 40: 60, filtering and separating the third oil-containing wax liquid to obtain a second-stage deoiling filtrate and a second-stage oil-containing wax liquid; and (3) mixing the material obtained after the fourth oil-containing wax liquid overflows through the deoiling filter with the second-stage oil-containing wax liquid obtained in the step 3), and recovering wax to obtain refined wax and a wax recovery solvent. The feeding temperature of the first-stage deoiling wax liquid is 0 ℃; diluting the third ketone-benzene dewaxing solvent and then carrying out cold washing, wherein the dilution ratio of the second-stage deoiling is 3.0, and the cold washing ratio of the second-stage deoiling is 0.5; the cold washing temperature of the two-stage deoiling is 0 ℃. Mixing the obtained second-stage oil-containing wax liquid and the fourth oil-containing wax liquid, recovering wax to obtain refined wax and a ketone-benzene dewaxing recovery solvent, and returning the obtained second-stage deoiled filtrate to the step 2), wherein the yield of the refined wax is 7.5%;
4) and (2) adsorbing the dewaxing filtrate obtained in the step 1) by using argil to obtain the white oil, wherein the using amount of the argil is 0.5 percent of the mass of the dewaxing filtrate obtained in the step 1), the reaction time is 90min, the feeding temperature is 80 ℃, the temperature of a white oil outlet device is 30 ℃, the yield of the white oil is 85 percent, and the performance index of the white oil is shown in table 1.
The first ketone benzene dewaxing solvent, the second ketone benzene dewaxing solvent and the third ketone benzene dewaxing solvent are a mixture of methyl ethyl ketone and toluene, and the content of the methyl ethyl ketone is 30 wt%.
The recovered solvent for ketone-benzene dewaxing can be returned to the step 1) for use.
The mass ratio of the fresh ketone-benzene dewaxing solvent to the ketone-benzene dewaxing recovered solvent used in the step 1) is 5: 1.
the ketone-benzene dewaxing process can be used for treating low-wax raw materials, the process is stable in operation, dewaxed oil with qualified freezing point is obtained, and the ketone-benzene dewaxing process for the low-wax raw materials is provided.
Example 2
A ketone-benzene dewaxing process for low wax content raw materials comprises the following steps:
1) dewaxing: diluting a low-wax raw material by using a first ketone-benzene dewaxing solvent for three times, then carrying out cold washing, and filtering and separating to obtain a dewaxing filtrate and an oil-containing wax liquid; the wax content of the low-wax raw material is 7 wt%, and the feeding temperature is 0 ℃; the primary ratio is 0.50; the secondary ratio is 2.5; the third ratio is 3.0; the cold washing ratio is 0.5, and the cold washing temperature is-15 ℃; the distillation range of the low-wax raw material is 315-367 ℃, the wax content is 7 wt%, the flash point is 167 ℃, and the freezing point is 9 ℃;
2) first-stage deoiling: diluting the oil-containing wax liquid obtained in the step 1) by using a second benzene dewaxing solvent, and then performing cold washing to obtain a mixture which is divided into a first oil-containing wax liquid and a second oil-containing wax liquid; the mass ratio of the first oil-containing wax liquid to the second oil-containing wax liquid is 70: 30, filtering and separating the first oil-containing wax liquid to obtain a first-stage deoiling filtrate and a first-stage deoiling wax liquid; the feeding temperature of the oil-containing wax liquid obtained in the step 1) is 10 ℃; the dilution ratio of the first-stage deoiling is 3.0; the cold washing ratio of the first-stage deoiling is 0.5; the cold washing temperature of the first-stage deoiling is 10 ℃; recovering the obtained first-stage deoiled filtrate by using wax oil to obtain wax oil and a ketone-benzene dewaxing recovery solvent, wherein the yield of the wax oil is 7.2%;
3) second-stage deoiling: the third ketone-benzene dewaxing solvent firstly dilutes the material of the first-stage deoiled wax liquid and the second oily wax liquid after overflowing through the deoiling filter, and then carries out cold washing, and the obtained mixture is divided into a third oily wax liquid and a fourth oily wax liquid; the mass ratio of the third oil-containing wax liquid to the fourth oil-containing wax liquid is 60: 40, filtering and separating the third oil-containing wax liquid to obtain a second-stage deoiling filtrate and a second-stage oil-containing wax liquid; and (3) mixing the material obtained after the fourth oil-containing wax liquid overflows through the deoiling filter with the second-stage oil-containing wax liquid obtained in the step 3), and recovering wax to obtain refined wax and a wax recovery solvent. The feeding temperature of the first-stage deoiling wax liquid is 10 ℃; diluting the third ketone-benzene dewaxing solvent and then carrying out cold washing, wherein the dilution ratio of the second-stage deoiling is 0.5, and the cold washing ratio of the second-stage deoiling is 2.0; the cold washing temperature of the two-stage deoiling is 10 ℃. And mixing the obtained second-stage oil-containing wax liquid and the fourth oil-containing wax liquid, and recovering wax to obtain refined wax and a ketone-benzene dewaxing recovery solvent. The obtained second-stage deoiled filtrate is returned to the step 2), and the yield of the refined wax is 7.1 percent.
4) And (2) adsorbing the dewaxing filtrate obtained in the step 1) by using argil to obtain the white oil, wherein the using amount of the argil is 3.5 percent of the mass of the dewaxing filtrate obtained in the step 1), the reaction time is 60min, the feeding temperature is 100 ℃, the temperature of a white oil outlet device is 45 ℃, the yield of the white oil is 85 percent, and the performance indexes of the white oil are shown in table 1.
The first ketone benzene dewaxing solvent, the second ketone benzene dewaxing solvent and the third ketone benzene dewaxing solvent are a mixture of methyl ethyl ketone and toluene, and the content of the methyl ethyl ketone is 80 wt%.
The recovered solvent for ketone-benzene dewaxing can be returned to the step 1) for use.
The mass ratio of the fresh ketone-benzene dewaxing solvent to the ketone-benzene dewaxing recovered solvent used in the step 1) is 1: 1.
the ketone-benzene dewaxing process can be used for treating low-wax raw materials, the process is stable in operation, dewaxed oil with qualified freezing point is obtained, and the ketone-benzene dewaxing process for the low-wax raw materials is provided.
Example 3
A ketone-benzene dewaxing process for low wax content raw materials comprises the following steps:
1) dewaxing: diluting a low-wax raw material by using a first ketone-benzene dewaxing solvent for three times, then carrying out cold washing, and filtering and separating to obtain a dewaxing filtrate and an oil-containing wax liquid; the wax content of the low-wax raw material is 5 wt%, and the feeding temperature is 20 ℃; the primary ratio is 2.0; the secondary ratio is 0.5; the third ratio is 0.5; the cold washing ratio is 2.0, and the cold washing temperature is-10 ℃; the distillation range of the low-wax raw material is 311-361 ℃, the wax content is 5 wt%, the flash point is 157 ℃, and the freezing point is 9 ℃;
2) first-stage deoiling: diluting the oil-containing wax liquid obtained in the step 1) by using a second benzene dewaxing solvent, and then performing cold washing to obtain a mixture which is divided into a first oil-containing wax liquid and a second oil-containing wax liquid; the mass ratio of the first oil-containing wax liquid to the second oil-containing wax liquid is 60: 40, filtering and separating the first oil-containing wax liquid to obtain a first-stage deoiling filtrate and a first-stage deoiling wax liquid; the feeding temperature of the oil-containing wax liquid obtained in the step 1) is 20 ℃; the dilution ratio of the first-stage deoiling is 1; the cold washing ratio of the first-stage deoiling is 0.9; the cold washing temperature of the first-stage deoiling is 20 ℃; recovering the obtained first-stage deoiled filtrate by using wax oil to obtain wax oil and a ketone-benzene dewaxing recovery solvent, wherein the yield of the wax oil is 6.4%;
3) second-stage deoiling: the third ketone-benzene dewaxing solvent firstly dilutes the material of the first-stage deoiled wax liquid and the second oily wax liquid after overflowing through the deoiling filter, and then carries out cold washing, and the obtained mixture is divided into a third oily wax liquid and a fourth oily wax liquid; the mass ratio of the third oil-containing wax liquid to the fourth oil-containing wax liquid is 50: 50, filtering and separating the third oil-containing wax liquid to obtain a second-stage deoiling filtrate and a second-stage oil-containing wax liquid; and (3) mixing the material obtained after the fourth oil-containing wax liquid overflows through the deoiling filter with the second-stage oil-containing wax liquid obtained in the step 3), and recovering wax to obtain refined wax and a wax recovery solvent. The feeding temperature of the first-stage deoiling wax liquid is 20 ℃; diluting the third ketone-benzene dewaxing solvent and then carrying out cold washing, wherein the dilution ratio of the second-stage deoiling is 1.6, and the cold washing ratio of the second-stage deoiling is 1.0; the cold washing temperature of the second-stage deoiling is 20 ℃; . And mixing the obtained second-stage oil-containing wax liquid and the fourth oil-containing wax liquid, and recovering wax to obtain refined wax and a ketone-benzene dewaxing recovery solvent. The obtained second-stage deoiled filtrate is returned to the step 2), and the yield of the refined wax is 8.3 percent.
4) And (2) adsorbing the dewaxing filtrate obtained in the step 1) by using argil to obtain the white oil, wherein the using amount of the argil is 5% of the mass of the dewaxing filtrate obtained in the step 1), the reaction time is 30min, the feeding temperature is 120 ℃, the temperature of a white oil outlet device is 60 ℃, the yield of the white oil is 85%, and the performance indexes of the white oil are shown in table 1.
The first ketone benzene dewaxing solvent, the second ketone benzene dewaxing solvent and the third ketone benzene dewaxing solvent are a mixture of methyl ethyl ketone and toluene, and the content of the methyl ethyl ketone is 60 wt%.
The recovered solvent for ketone-benzene dewaxing can be returned to the step 1) for use.
The mass ratio of the fresh ketone-benzene dewaxing solvent to the ketone-benzene dewaxing recovered solvent used in the step 1) is 3: 1.
the ketone-benzene dewaxing process can be used for treating low-wax raw materials, the process is stable in operation, dewaxed oil with qualified freezing point is obtained, and the ketone-benzene dewaxing process for the low-wax raw materials is provided.
TABLE 1
| Index of white oil | Example 1 | Example 2 | Example 3 |
| Kinematic viscosity (40 ℃), mm2/s | 7.746 | 7.956 | 7.780 |
| Kinematic viscosity (100 ℃) mm2/s | 2.242 | 2.248 | 2.451 |
| Flash point (closed mouth), deg.C | 171 | 153 | 160 |
| Pour point, DEG C | -23 | -24 | -24 |
| Mechanical impurities and moisture | Is free of | Is free of | Is free of |
| Color (Sai's), number | +10 | +5 | +5 |
| Viscosity index | 95 | 83 | 98 |
| Sulfur content/(mg/kg) | 0.0012 | 0.0244 | 0.0006 |
| Organic solvent content | 10ppm | 12ppm | 15ppm |
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (13)
1. The preparation method of the white oil is characterized by comprising the following steps:
1) dewaxing: mixing a low-wax raw material with a first ketobenzene dewaxing solvent, and then filtering and separating to obtain a dewaxing filtrate and an oil-containing wax liquid;
2) first-stage deoiling: mixing the oil-containing wax liquid obtained in the step 1) with a second benzol dewaxing solvent, and then dividing the mixture into a first oil-containing wax liquid and a second oil-containing wax liquid, wherein the mass ratio of the first oil-containing wax liquid to the second oil-containing wax liquid is 50-70: 30-50, filtering and separating the first oil-containing wax liquid to obtain a first-stage deoiled filtrate and a first-stage deoiled wax liquid;
3) second-stage deoiling: mixing the first-stage deoiled wax liquid, the second oil-containing wax liquid and a third ketone-benzene dewaxing solvent, and then dividing the mixture into a third oil-containing wax liquid and a fourth oil-containing wax liquid, wherein the mass ratio of the third oil-containing wax liquid to the fourth oil-containing wax liquid is 40-60: 40-60, filtering and separating the third oil-containing wax liquid to obtain a second-stage deoiling filtrate and a second-stage oil-containing wax liquid;
4) clay refining: carrying out clay adsorption on the dewaxing filtrate obtained in the step 1) to obtain the white oil;
the distillation range of the low-wax raw material is 250-360 ℃, the wax content is less than or equal to 12 wt%, the flash point is 150-170 ℃, and the freezing point is 6-14 ℃;
in the step 1), diluting a first ketone-benzene dewaxing solvent for three times, and then carrying out cold washing, wherein the first time ratio is 0.5-2.0, the second time ratio is 0.5-2.5, the third time ratio is 0.5-3.0, the cold washing ratio is 0.5-2.0, and the cold washing temperature is-20 to-10 ℃;
in the step 2), the second benzene dewaxing solvent is diluted firstly and then is subjected to cold washing, the dilution ratio of the first-stage deoiling is 0.5-3.0, and the cold washing ratio of the first-stage deoiling is 0.5-2.0;
in the step 3), the third ketone-benzene dewaxing solvent is diluted firstly and then subjected to cold washing, the dilution ratio of the second-stage deoiling is 0.5-3.0, and the cold washing ratio of the second-stage deoiling is 0.5-2.0.
2. The method of claim 1, wherein the first, second and third ketone-benzene dewaxing solvents are a mixture of methyl ethyl ketone and toluene, and the methyl ethyl ketone content is 30-80 wt%.
3. The method of claim 1, wherein step 1) further comprises one or more of the following features:
1) the feeding temperature of the low-wax raw material is-25-20 ℃;
2) the mass ratio of the first ketone-benzene dewaxing solvent to the low-wax raw material is 2-9.5.
4. The method of claim 1, wherein step 2) further comprises one or more of the following features:
1) the feeding temperature of the oil-containing wax liquid obtained in the step 1) is 0-20 ℃;
2) the mass ratio of the second diketone benzene dewaxing solvent to the oily wax liquid obtained in the step 1) is 1-5;
3) the cold washing temperature of the first-stage deoiling is 0-20 ℃.
5. The method of claim 1, wherein step 3) further comprises one or more of the following features:
1) the feeding temperature of the first-stage deoiling wax liquid is 0-20 ℃;
2) the mass ratio of the total mass of the first-stage deoiled wax liquid and the second oil-containing wax liquid to the third ketone-benzene dewaxing solvent is 1: 1-5;
3) the cold washing temperature of the two-stage deoiling is 0-20 ℃.
6. The method of claim 1, further comprising one or more of the following features:
1) recovering the dewaxing filtrate obtained in the step 1) to obtain dewaxed oil and a ketone-benzene dewaxing recovered solvent;
2) recovering the first-stage deoiled filtrate obtained in the step 2) through wax oil to obtain wax oil and a ketone-benzene dewaxing recovery solvent;
3) mixing the second-stage oil-containing wax liquid obtained in the step 3) with the fourth oil-containing wax liquid, and recovering wax to obtain refined wax and a ketone-benzene dewaxing recovery solvent.
7. The method for preparing the white oil according to claim 6, wherein the dewaxing oil of claim 1) has a freezing point of-24 to-3 ℃ and a content of the benzol ketone dewaxing solvent in the dewaxing oil of 0 to 100 mg/kg.
8. The method for preparing the white oil according to claim 6, wherein in the step 3), the material obtained by overflowing the fourth oily wax liquid through the deoiling filter is mixed with the second-stage oily wax liquid obtained in the step 3), and the refined wax and the wax recovery solvent are obtained through wax recovery.
9. The method of producing a white oil according to claim 6, wherein one or more solvents selected from the group consisting of the recovered solvent by acetone dewaxing in characteristic 1), the recovered solvent by acetone dewaxing in characteristic 2), and the recovered solvent by acetone dewaxing in characteristic 3) are returned to step 1) for use.
10. The method for preparing the white oil according to claim 9, wherein the mass ratio of the fresh ketone-benzene dewaxing solvent to the recovered ketone-benzene dewaxing solvent used in the returning step 1) is 1-5: 1.
11. the method for preparing a white oil according to claim 1, wherein in the step 3), the first-stage deoiled wax liquid, the ketone-benzene dewaxing solvent and the second oil-containing wax liquid are separated into a third oil-containing wax liquid and a fourth oil-containing wax liquid after being mixed with each other and overflowing through the deoiling filter.
12. The method for preparing white oil according to claim 1, wherein the secondary de-oiling filtrate obtained in step 3) is returned to step 2).
13. The method of claim 1, wherein step 4) further comprises one or more of the following features:
1) the using amount of the argil is 0.5-5% of the mass of the dewaxing filtrate obtained in the step 1);
2) the reaction time is 30-90 min;
3) the feeding temperature is 80-120 ℃;
4) the temperature of the white oil discharged from the device is 30-60 ℃.
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