CN111171863A - Method for preparing high-purity isoparaffin from normal paraffin - Google Patents
Method for preparing high-purity isoparaffin from normal paraffin Download PDFInfo
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- CN111171863A CN111171863A CN202010008933.0A CN202010008933A CN111171863A CN 111171863 A CN111171863 A CN 111171863A CN 202010008933 A CN202010008933 A CN 202010008933A CN 111171863 A CN111171863 A CN 111171863A
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- 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
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing high-purity isoparaffin by using normal paraffin, which comprises the following steps: 1) mixing and heating normal alkane and hydrogen to contact with a catalyst I for isomerization reaction; 2) heating the reaction product obtained in the step 1), and then contacting the reaction product with a catalyst II to perform hydrogenation and dearomatization reaction, and removing aromatic hydrocarbon in the product; 3) contacting the product of removing the aromatic hydrocarbon in the step 2) with a catalyst III to carry out hydrogenation addition reaction; the method is suitable for liquid wax and partial paraffin oil products with high pour point, poor viscosity-temperature index and high n-alkane content, has the advantages of wide application range, strong reaction treatment capacity, high separation precision and the like, and can separate different types of heterogeneous white oil products according to the properties of raw materials and the distillation range characteristics.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a method for preparing high-purity isoparaffin by using normal paraffin.
Background
The solvent oil product is one of five major petroleum products, and can be divided into aromatic hydrocarbon, dearomatized aliphatic group, isomeric alkane, naphthenic hydrocarbon, normal alkane and the like, wherein the isomeric alkane solvent oil has the characteristics of low condensation point, small smell, low toxicity, good stability and the like, and is widely used for printing and dyeing diluents, printing ink solvents, metal processing cleaning agents, anti-rust oil, odorless spray, paint organosol formulas, high-grade clothes dry cleaning oil, peroxide organic compound carriers, washing daily chemical products and the like. With the influence of national environmental protection hurricanes, all industries shuffle cards again, high-pollution and non-regular enterprises are eliminated completely, and meanwhile, the pursuit of consumers for high-quality life at present also forces production enterprises and merchants to provide products which are more environmental-friendly and harmless to human health.
In 1995, the demand of China for environment-friendly solvent oil is less than 2 ten thousand tons, in 2010, the demand rises to 42 ten thousand tons, and in 2017, the number of the environment-friendly solvent oil exceeds 60 ten thousand tons. The demand of the isoparaffin solvent oil as the top product of the pyramid of the environment-friendly solvent oil is also increased year by year from less than 3000 tons in the 90 s to the current demand of 7 ten thousand tons. Moreover, with the continuous enhancement of the national environmental protection policy, the demand of isoparaffin solvent oil will increase beyond imagination. The production process mainly comprises the following steps: firstly, a chemical synthesis technology; secondly, a coal Fischer-Tropsch synthesis and adsorption separation technology; and thirdly, utilizing catalyst for conversion, namely catalytic reforming.
Chemical synthesis is used for producing isoparaffin by designing a chemical reaction process, the produced isoparaffin has high purity and basically has no impurities, but the raw material requirement is high, and meanwhile, the production process is extremely strict and is difficult to be applied and popularized in large-scale continuous industrial production. The technical and investment requirements are great.
The Fischer-Tropsch synthesis technology for coal is a main method for producing isoparaffin in China at present, but the technology has defects compared with the traditional chemical synthesis technology, because the coal oil has unknown components and is inferior to the chemical synthesis technology in chemical stability. Meanwhile, the adsorption separation of the molecular sieve is required in the subsequent working section, and the process is complex.
Compared with other methods, the method utilizes catalyst conversion, develops a new metal composition formula of the hydrotreating catalyst by customizing a catalyst carrier, and produces high-purity isoparaffin by carrying out hydro-isomerization and post-hydrogenation refined hydrotreating processes on normal paraffin. The method has the advantages of advanced technology, high product yield, high quality, low cost, no three-waste pollution, continuous production and the like. How to select a proper process method to produce high-purity isoparaffin products is the subject of the worldwide research nowadays.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: a method for preparing high-purity isoparaffin from normal paraffin is provided. The method is suitable for liquid wax and partial paraffin oil products with high pour point, poor viscosity-temperature index and high n-alkane content, has the advantages of wide application range, strong reaction treatment capacity, high separation precision and the like, and can separate different types of heterogeneous white oil products according to the properties of raw materials and the distillation range characteristics.
The technical solution of the invention is as follows: a method for preparing high-purity isoparaffin by using normal paraffin comprises the following steps:
1) mixing and heating normal alkane and hydrogen to reaction temperature, and introducing the mixture into a fixed bed isomerization reactor loaded with a catalyst I to contact with the catalyst I for isomerization reaction; during reaction, n-alkane molecules enter the pore channels of the molecular sieve of the catalyst I, and are contacted with active metal, the molecules are subjected to hydrogenolysis under the action of hydrogen, the molecular chain segments after hydrogenolysis are grafted on the main chain in a short time, and hydrogen is removed simultaneously, so that hydrogen participates in the reaction in the whole process, but no consumption is generated. Side reaction exists when the isomerization reaction occurs, a small amount of aromatic hydrocarbon and cyclane carry out ring opening reaction, a small amount of cracking reaction carries out isomerization on oil, and a small amount of olefin is generated.
2) Heating the reaction product obtained in the step 1), introducing the heated reaction product into a fixed bed noble metal dearomatization reactor loaded with a catalyst II to contact with the catalyst II for hydrogenation dearomatization reaction, and removing aromatic hydrocarbon in the product;
3) and (3) introducing the product of which the aromatic hydrocarbon is removed in the step 2) into a fixed bed complementary delicate reactor loaded with a catalyst III to contact with the catalyst III for hydrogenation addition reaction, carrying out capture addition on ultra-low trace olefin and aromatic hydrocarbon, carrying out addition reaction on unsaturated hydrocarbon in the ultra-low trace olefin and aromatic hydrocarbon, and finely cutting the obtained reactant through a fractionating system to obtain various high-purity isomeric white oil products with different brands.
The normal alkane: the initial boiling point is 100-200 ℃, the final boiling point is 300-450 ℃, the density at 20 ℃ is 720-900 kg/m, the content of aromatic hydrocarbon is no more than 0.1 percent, the content of sulfur is no more than 1.0 mu g/g, the content of nitrogen is no more than 2.0 mu g/g, the content of asphaltene is no more than 100 mu g/g, and the pour point is 0-20 ℃.
Further, the reaction conditions of the isomerization reaction in the step 1) are as follows: the reaction temperature is 250-400 ℃, the reaction pressure is 4-16 Mpa, and the volume space velocity is 0.2-1.4 h-1The volume ratio of hydrogen to oil is 400-2400: 1.
further, the reaction conditions of step 2) and step 3) are as follows: the reaction temperature is 150-320 ℃, the reaction pressure is 4-16 Mpa, and the volume space velocity is 0.2-1.4 h-1The volume ratio of hydrogen to oil is 400-2400: 1.
further, the reaction conditions of step 1) are as follows: the reaction temperature is 300 ℃, the reaction pressure is 9Mpa, and the volume space velocity is 0.8h-1And the volume ratio of hydrogen to oil is 800: 1.
Further, the reaction conditions of step 2) are as follows: the reaction temperature is 200 ℃, the reaction pressure is 9Mpa, and the volume space velocity is 0.8h-1And the volume ratio of hydrogen to oil is 800: 1.
Further, the reaction conditions of step 3) are as follows: the reaction temperature is 200 ℃, the reaction pressure is 9Mpa, and the volume space velocity is 0.8h-1And the volume ratio of hydrogen to oil is 800: 1.
Further, the catalyst I is a noble metal Pt or La type catalyst, the pore volume of the selected carrier is 0.12-0.35 ml/g, and the specific surface area is 150-240 m2/g。
Further, the catalyst II is a noble metal Pt or Pd type catalyst, the pore volume of the selected carrier is 0.30-0.90 ml/g, and the specific surface area is 180-380 m2/g。
Further, the catalyst III is a Ni type catalyst, the pore volume of the selected carrier is 0.30-0.90 ml/g, and the specific surface area is 180-380 m2/g。
The invention has the beneficial effects that: the invention has wide distillation range of the raw material normal paraffin, wide application range, can produce the paraffin-based oil into an isomeric product with higher added value, and has obvious economic benefit.
The method combines specific reaction conditions and the type of the catalyst with corresponding specific surface area, is suitable for liquid wax and partial paraffin oil products with high pour point, poor viscosity-temperature index and high n-alkane content, has the advantages of wide application range, strong reaction treatment capacity, high separation precision and the like, and can separate different types of isomeric white oil products according to the properties of raw materials and the distillation range characteristics.
The high-purity isomeric white oil produced by the invention meets the standard requirement of food-grade white oil, the content of aromatic hydrocarbon is not more than 0.001 percent, the content of sulfur is not more than 1mg/kg, the pour point is not more than-40 ℃, the bromine index is not more than 10mgBr/100g, and the content of isomeric hydrocarbon is more than 90 percent.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Examples
The method for preparing high-purity isoparaffin by using normal paraffin comprises the following steps:
step one, hydroisomerization
The method comprises the steps of mixing n-alkane with hydrogen, heating the mixture in a heating furnace through a heat exchanger, heating the mixture to a reaction temperature, feeding the heated mixture into an isomerization reactor loaded with a catalyst I, and carrying out an isomerization reaction in the isomerization reactor by contacting the catalyst I with the catalyst I, wherein the catalyst I is a noble metal Pt or La type catalyst, the pore volume is 0.12-0.35 ml/g, and the specific surface area is 150-240 m2And/g, during reaction, n-alkane molecules enter pore channels of the molecular sieve of the catalyst I with a certain spatial structure, the molecules are subjected to hydrogenolysis under the action of hydrogen through contact with active metal, the molecular chain segments after hydrogenolysis are grafted on a main chain in a short time, hydrogen is removed simultaneously, and the hydrogen participates in the reaction in the whole process but is not consumed. Side reaction exists when the isomerization reaction occurs, a small amount of aromatic hydrocarbon and cyclane carry out ring opening reaction, a small amount of cracking reaction carries out isomerization on oil, and a small amount of olefin is generated;
the reaction conditions of the first step are as follows: the reaction temperature is 300 ℃, the reaction pressure is 9Mpa, and the volume space velocity is 0.8h-1And the volume ratio of hydrogen to oil is 800: 1.
The properties of the n-alkanes are shown in the following table:
TABLE 1 Normal alkane feedstock Properties
Step two, aromatic hydrocarbon saturation
The product after reaction in the isomerization reactor enters a dearomatization reactor loaded with a catalyst II after heat exchange through a heat exchanger, and is in contact with the catalyst II in the dearomatization reactor for hydrofining reaction, wherein the catalyst II is a noble metal Pt or Pd type catalyst, the pore volume is 0.30-0.90 ml/g, and the specific surface area is 180-380 m2(g), performing addition reaction on aromatic hydrocarbon in the reaction solution;
the reaction conditions of the second step are as follows: the reaction temperature is 200 ℃, the reaction pressure is 9Mpa, and the volume space velocity is 0.8h-1And the volume ratio of hydrogen to oil is 800: 1.
Step three, supplementing refinement
Directly feeding a product obtained after reaction in the fixed bed noble metal dearomatization reactor into a fixed bed supplementary delicate reactor loaded with a catalyst III, contacting the product with the catalyst III in the reactor to carry out hydrogenation addition reaction, carrying out capture addition on ultra-low trace olefin and aromatic hydrocarbon, and carrying out addition reaction on unsaturated hydrocarbon in the ultra-low trace olefin and aromatic hydrocarbon;
step four, fractional distillation
And D, allowing the reactant obtained in the step three to enter a fractionation system for fine cutting to obtain various high-purity isomeric white oil products with different brands.
The properties of the high purity isomeric white oil product produced by the present invention are shown in the following table:
TABLE 2 Isoalkane product Properties
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (10)
1. A method for preparing high-purity isoparaffin by using normal paraffin is characterized by comprising the following steps:
1) mixing and heating normal alkane and hydrogen to reaction temperature, and introducing the mixture into a fixed bed isomerization reactor loaded with a catalyst I to contact with the catalyst I for isomerization reaction;
2) heating the reaction product obtained in the step 1), introducing the heated reaction product into a fixed bed noble metal dearomatization reactor loaded with a catalyst II to contact with the catalyst II for hydrogenation dearomatization reaction, and removing aromatic hydrocarbon in the product;
3) and (3) introducing the product of which the aromatic hydrocarbon is removed in the step 2) into a fixed bed complementary delicate reactor loaded with a catalyst III to contact with the catalyst III for hydrogenation addition reaction, carrying out capture addition on ultra-low trace olefin and aromatic hydrocarbon, carrying out addition reaction on unsaturated hydrocarbon in the ultra-low trace olefin and aromatic hydrocarbon, and finely cutting the obtained reactant through a fractionating system to obtain various high-purity isomeric white oil products with different brands.
2. The method for preparing high-purity isoparaffin according to claim 1, wherein the normal paraffin: the initial boiling point is 100-200 ℃, the final boiling point is 300-450 ℃, the density at 20 ℃ is 720-900 kg/m, the content of aromatic hydrocarbon is no more than 0.1 percent, the content of sulfur is no more than 1.0 mu g/g, the content of nitrogen is no more than 2.0 mu g/g, the content of asphaltene is no more than 100 mu g/g, and the pour point is 0-20 ℃.
3. The method for preparing high-purity isoparaffin from normal paraffin according to claim 1, wherein the reaction conditions of the isomerization reaction in step 1) are: the reaction temperature is 250-400 ℃, the reaction pressure is 4-16 Mpa, and the volume space velocity is 0.2-1.4 h-1The volume ratio of hydrogen to oil is 400-2400: 1.
4. the method for preparing high-purity isoparaffin according to claim 1, wherein the reaction conditions of step 2) and step 3) are as follows: the reaction temperature is 150-320 ℃, the reaction pressure is 4-16 Mpa, and the volume space velocity is 0.2-1.4h-1The volume ratio of hydrogen to oil is 400-2400: 1.
5. the method for preparing high-purity isoparaffin according to claim 1, wherein the reaction conditions in step 1) are as follows: the reaction temperature is 300 ℃, the reaction pressure is 9Mpa, and the volume space velocity is 0.8h-1And the volume ratio of hydrogen to oil is 800: 1.
6. The method for preparing high-purity isoparaffin according to claim 1, wherein the reaction conditions in step 2) are as follows: the reaction temperature is 200 ℃, the reaction pressure is 9Mpa, and the volume space velocity is 0.8h-1And the volume ratio of hydrogen to oil is 800: 1.
7. The method for preparing high-purity isoparaffin according to claim 1, wherein the reaction conditions in step 3) are as follows: the reaction temperature is 200 ℃, the reaction pressure is 9Mpa, and the volume space velocity is 0.8h-1And the volume ratio of hydrogen to oil is 800: 1.
8. The method for preparing high-purity isoparaffin from normal paraffin according to claim 1, wherein the catalyst I is a noble metal Pt, La type catalyst, the pore volume of the carrier is 0.12-0.35 ml/g, and the specific surface area is 150-240 m2/g。
9. The method for preparing high-purity isoparaffin according to claim 1, wherein the catalyst II is a noble metal catalyst of Pt or Pd type, the pore volume of the carrier is 0.30-0.90 ml/g, and the specific surface area is 180-380 m2/g。
10. The method for preparing high-purity isoparaffin according to claim 1, wherein the catalyst III is Ni type catalyst, the pore volume of the carrier is 0.30-0.90 ml/g, and the specific surface area is 180-380 m2/g。
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| CN202010008933.0A CN111171863A (en) | 2020-01-06 | 2020-01-06 | Method for preparing high-purity isoparaffin from normal paraffin |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1952066A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Hydrogenation process of producing food-level white oil |
| CN107987881A (en) * | 2017-11-30 | 2018-05-04 | 中海沥青股份有限公司 | A kind of preparation method of thick white oil |
| CN110041962A (en) * | 2019-04-22 | 2019-07-23 | 洛阳金达石化有限责任公司 | A method of by subtracting the high viscous white oil of base oil production |
| CN209797876U (en) * | 2019-04-22 | 2019-12-17 | 洛阳金达石化有限责任公司 | Device for producing high-viscosity white oil by bottom reducing oil |
-
2020
- 2020-01-06 CN CN202010008933.0A patent/CN111171863A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1952066A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Hydrogenation process of producing food-level white oil |
| CN107987881A (en) * | 2017-11-30 | 2018-05-04 | 中海沥青股份有限公司 | A kind of preparation method of thick white oil |
| CN110041962A (en) * | 2019-04-22 | 2019-07-23 | 洛阳金达石化有限责任公司 | A method of by subtracting the high viscous white oil of base oil production |
| CN209797876U (en) * | 2019-04-22 | 2019-12-17 | 洛阳金达石化有限责任公司 | Device for producing high-viscosity white oil by bottom reducing oil |
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