CN114634825B - Method for dearomatizing heavy pyrolysis gasoline and producing white oil - Google Patents
Method for dearomatizing heavy pyrolysis gasoline and producing white oil Download PDFInfo
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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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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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
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a method for dearomatizing heavy pyrolysis gasoline and producing white oil, which comprises (1) adding a modified doped RE-USY molecular sieve as a promoting catalyst into a heavy pyrolysis gasoline raw material, and carrying out pretreatment reaction at 0.6-1.0MPa, 210-260 ℃ and a volume airspeed of 2-5h < -1 >; (2) extraction: adding an extractant into the aromatic hydrocarbon crude product, and extracting for 6-8min at 74-86 ℃ with a reflux ratio of 0.5-2:1, respectively obtaining an aromatic-rich product and a non-aromatic product; (3) And taking a non-aromatic hydrocarbon product, carrying out liquid phase reaction, and carrying out gas-liquid separation to obtain crude white oil. The invention also provides a preparation method of the modified doped RE-USY molecular sieve promoted catalyst and the extractant. The purity of the aromatic hydrocarbon-rich product obtained by the method reaches 97.3%, the chromaticity is 6.0, the liquefied gas yield is 22.5%, the sulfur content of the crude white oil is 0.16% by weight, the utilization value of the heavy pyrolysis gasoline is further improved, and the pretreatment reaction and extraction process conditions are mild, so that the method is an ideal and environment-friendly production method.
Description
Technical Field
The invention relates to the technical field of heavy pyrolysis gasoline, in particular to a method for dearomatizing heavy pyrolysis gasoline and producing white oil.
Background
Aromatic hydrocarbon is a general term of hydrocarbon containing benzene ring structure, is one of industrial basic raw materials, especially benzene, toluene and xylene in aromatic hydrocarbon, is an important raw material for petrochemical industry in China, and the demand is inferior to ethylene and propylene. Meanwhile, with the development of the polyester industry, the demand of upstream raw material dimethylbenzene is driven, but the self-supply rate of the dimethylbenzene productivity in China is not high. Therefore, various aromatic hydrocarbon process production routes are necessary for layout construction.
Aromatic hydrocarbons are mainly from petroleum and coal tar, naphtha is mainly used as a raw material, and an aromatic hydrocarbon combination device is adopted for production. At present, domestic mature aromatic hydrocarbon production technologies are as follows: catalytic reforming of produced oil, hydrogenation of pyrolysis gasoline as a byproduct of steam cracking, aromatization of light hydrocarbons, disproportionation and transalkylation of toluene/benzene, preparation of aromatic hydrocarbon from coal, and the like. Heavy aromatics in heavy resources such as heavy pyrolysis gasoline and catalytic cracking light cycle oil are utilized to improve the productivity of aromatics through reactions such as lightening, hydrocracking and the like, so that on one hand, the problem of insufficient supply of naphtha raw materials can be solved, and on the other hand, the utilization rate of the heavy pyrolysis gasoline can be improved.
The pyrolysis gasoline is an important product in ethylene industry, the aromatic hydrocarbon content reaches more than 60%, the pyrolysis gasoline can be used for producing aromatic hydrocarbon of organic chemical raw materials, meanwhile, the pyrolysis gasoline also contains a large amount of unsaturated hydrocarbon, sulfur and other compounds, the components can greatly reduce the selectivity of an extractant when extracting aromatic hydrocarbon, and the purity and chromaticity of an aromatic hydrocarbon product can be seriously influenced. In recent years, along with the expansion of ethylene productivity, the cracking raw materials are diversified, so that the composition of the cracking gasoline is complex and changeable, and the content of sulfur, arsenic, nitrogen and other impurities in part of raw materials is higher, which puts higher demands on the production of aromatic hydrocarbon by using the cracking gasoline. White oil is a liquid hydrocarbon mixture obtained by refining petroleum, mainly saturated naphthene and paraffin mixtures. When the pyrolysis gasoline is utilized to extract aromatic hydrocarbon, the non-aromatic hydrocarbon component obtained by dearomatization is reused for preparing white oil, so that the pyrolysis gasoline can be utilized more fully, and the industrial productivity is further improved.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for dearomatizing heavy pyrolysis gasoline and producing white oil, which solves the above problems.
The technical scheme of the invention is realized as follows:
a method for dearomatizing heavy pyrolysis gasoline and producing white oil, comprising the following steps:
(1) Pretreatment: the modified doping type RE-USY molecular sieve is used as a promoting catalyst, and the mass ratio is 0.27-0.36:1, adding the mixture into a heavy pyrolysis gasoline raw material, and controlling the volume airspeed to be 2-5h at the temperature of 210-260 ℃ and the pressure of 0.6-1.0MPa -1 Carrying out pretreatment reaction, and carrying out pretreatment reaction for removing other impurities such as olefin, nitrogen and the like to obtain an aromatic crude product;
(2) Extraction: the mass ratio is 1:0.08-0.12, adding extractant into the crude product of aromatic hydrocarbon, extracting for 6-8min at 74-86 ℃, and the reflux ratio is 0.5-2:1, respectively obtaining an aromatic-rich product and a non-aromatic product;
(3) And (3) a finished product: and taking a non-aromatic hydrocarbon product, carrying out liquid phase reaction, and carrying out gas-liquid separation to obtain crude white oil.
Further describing, the preparation method of the promoting catalyst comprises the following steps: adding RE-USY molecular sieve into sodium carbide aluminate solution, heating and reacting to obtain modified RE-USY molecular sieve; and mixing the metal oxide precursor solution with a binder, and adding the modified RE-USY molecular sieve, and roasting at high temperature to obtain the modified doped RE-USY molecular sieve.
Still further described, the preparation method of the promoting catalyst comprises the following steps:
(a1) Weighing the following raw materials in parts by weight: 23-33 parts of RE-USY molecular sieve, 50-70 parts of sodium carbide aluminate solution, 16-28 parts of metal oxide and 7-12 parts of binder;
(a2) Adding RE-USY molecular sieve into sodium carbide aluminate solution, regulating pH value to 6.5-6.9, reacting at 60-70 deg.C for 1-2 hr, filtering and stoving to obtain modified RE-USY molecular sieve;
(a3) Mixing the metal oxide precursor solution with a binder, stirring for 4-6 hours, adding a modified RE-USY molecular sieve, drying, and roasting at 300-400 ℃ for 5-8 hours to obtain the modified doped RE-USY molecular sieve.
Further illustratively, the binder is a polyvinyl acetate emulsion; the metal oxide consists of potassium oxide and sodium oxide; the metal oxide precursor solution has a potassium/sodium molar ratio of 1:2-3.
Further illustratively, in step (a 2), the pH is adjusted to a pH of from 6.7 to 6.8.
Further described, the preparation method of the extractant comprises the following steps:
(b1) Weighing the following raw materials in parts by weight: 10-16 parts of porous alumina, 4-9 parts of tetraglyme, 12-18 parts of propylene carbonate and 20-30 parts of sodium hydroxide solution;
(b2) Mixing tetraglyme and propylene carbonate to obtain a mixed solvent;
(b3) Mixing porous alumina and sodium hydroxide solution, stirring at 40-50deg.C for 30-40min, adding mixed solvent, and stirring to obtain extractant.
The invention selects porous alumina, tetraglyme, propylene carbonate and sodium hydroxide solution to prepare the extractant, and has excellent solvent solubility at a certain temperature, is not easy to cause the conditions of dirt agglomeration and sieve pore blocking in the extraction process, and can avoid the phenomenon of complete mutual dissolution, thereby increasing non-aromatic components in the solvent and affecting the purification efficiency.
Further, in the step (2), the extraction temperature is 82 ℃ and the extraction time is 7min.
Further, in the step (2), the mass ratio of the aromatic hydrocarbon crude product to the extractant is 1:0.1.
further, in the step (1), the pressure of the pretreatment reaction is 0.7-0.8MPa, and the temperature of the pretreatment reaction is 230-240 ℃.
Further illustratively, in step (1), the mass ratio of the promoting catalyst to the pretreated heavy pyrolysis gasoline is 0.32:1.
compared with the prior art, the invention has the beneficial effects that:
the invention respectively controls the condition parameters of pretreatment reaction and extraction process through pretreatment, dearomatization, extraction and liquid phase reaction of heavy pyrolysis gasoline raw materials, takes a modified doped RE-USY molecular sieve as a promoting catalyst, and preferably promotes the catalyst dosage, and simultaneously ensures that the purity of the obtained aromatic-rich product reaches 97.3 percent, the chromaticity is 6.0, the liquefied gas yield is 22.5 percent, the sulfur content of crude white oil is 0.16 weight percent, the national standard requirement is met, the utilization value of the heavy pyrolysis gasoline is further improved, and the productivity of aromatic hydrocarbon is increased through reasonably preparing the extractant and controlling the dosage; the pretreatment reaction and the extraction process of the invention have mild conditions, and are ideal and environment-friendly production methods.
In addition, the RE-USY molecular sieve, the sodium carbide aluminate solution, the metal oxide and the binder are adopted to prepare the modified doped RE-USY molecular sieve as a promoting catalyst, so that the reactions such as rapid desulfurization, dearomatization and the like can be realized at a lower temperature, the decomposition of sulfide, nitride and other impurities is promoted, the removal of the impurities is facilitated, the chromaticity of the aromatic-rich product after extraction separation and the sulfur content of crude white oil are reduced, and meanwhile, the dearomatization reaction of the raw materials can be promoted, the subsequent extraction separation is facilitated, and the high-purity aromatic-rich product is obtained; the invention adopts metal oxide potassium oxide and sodium oxide to prepare the modified K/Na doped RE-USY molecular sieve, can increase the selectivity of the RE-USY molecular sieve for directionally converting light aromatic hydrocarbon, improves the stability of the promotion catalyst, and further improves the purity of the aromatic hydrocarbon-rich product.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
A method for dearomatizing heavy pyrolysis gasoline and producing white oil, comprising the following steps:
(1) Pretreatment: the modified doping type RE-USY molecular sieve is used as a promoting catalyst, and the mass ratio is 0.27:1, adding the mixture into a heavy pyrolysis gasoline raw material, and controlling the volume space velocity to be 2h at the temperature of 210 ℃ under 0.6MPa -1 Carrying out pretreatment reaction to obtain an aromatic hydrocarbon crude product;
(2) Extraction: the mass ratio is 1:0.08, adding an extractant into the aromatic crude product, extracting for 6min at 74 ℃, wherein the reflux ratio is 0.5:1, respectively obtaining an aromatic-rich product and a non-aromatic product;
(3) And (3) a finished product: taking a non-aromatic hydrocarbon product, carrying out liquid phase reaction, and carrying out gas-liquid separation to obtain crude white oil;
the preparation method of the promotion catalyst comprises the following steps:
(a1) The following raw materials by weight are taken: 28g of RE-USY molecular sieve, 60g of sodium carbide aluminate solution, 22g of metal oxide and 9g of binder;
(a2) Adding RE-USY molecular sieve into sodium carbide aluminate solution, regulating pH value to 6.8, reacting at 65 ℃ for 2 hours, filtering and drying to obtain modified RE-USY molecular sieve;
(a3) Mixing the metal oxide precursor solution with a binder, stirring for 5 hours, adding a modified RE-USY molecular sieve, drying, and roasting at 350 ℃ for 6 hours to obtain a modified K/Na doped RE-USY molecular sieve;
wherein the binder is polyvinyl acetate emulsion; the metal oxide consists of potassium oxide and sodium oxide; the metal oxide precursor solution had a potassium/sodium molar ratio of 1:2;
the preparation method of the extractant comprises the following steps:
(b1) The following raw materials by weight are taken: 13g of porous alumina, 6g of tetraglyme, 14g of propylene carbonate and 25g of sodium hydroxide solution;
(b2) Mixing tetraglyme and propylene carbonate to obtain a mixed solvent;
(b3) Mixing porous alumina and sodium hydroxide solution, stirring at 45deg.C for 35min, adding mixed solvent, and stirring to obtain extractant.
Example 2
A method for dearomatizing heavy pyrolysis gasoline and producing white oil, comprising the following steps:
(1) Pretreatment: the modified doping type RE-USY molecular sieve is used as a promoting catalyst, and the mass ratio is 0.36:1, adding the mixture into a heavy pyrolysis gasoline raw material, and controlling the volume space velocity at 1.0MPa and 260 ℃ for 5h -1 Carrying out pretreatment reaction to obtain an aromatic hydrocarbon crude product;
(2) Extraction: the mass ratio is 1:0.12, adding an extractant into the aromatic crude product, extracting for 8min at 86 ℃, wherein the reflux ratio is 2:1, respectively obtaining an aromatic-rich product and a non-aromatic product;
(3) And (3) a finished product: taking a non-aromatic hydrocarbon product, carrying out liquid phase reaction, and carrying out gas-liquid separation to obtain crude white oil;
the preparation method of the promotion catalyst comprises the following steps:
(a1) The following raw materials by weight are taken: 28g of RE-USY molecular sieve, 60g of sodium carbide aluminate solution, 22g of metal oxide and 9g of binder;
(a2) Adding RE-USY molecular sieve into sodium carbide aluminate solution, regulating pH value to 6.8, reacting at 65 ℃ for 2 hours, filtering and drying to obtain modified RE-USY molecular sieve;
(a3) Mixing the metal oxide precursor solution with a binder, stirring for 5 hours, adding a modified RE-USY molecular sieve, drying, and roasting at 350 ℃ for 6 hours to obtain a modified K/Na doped RE-USY molecular sieve;
wherein the binder is polyvinyl acetate emulsion; the metal oxide consists of potassium oxide and sodium oxide; the metal oxide precursor solution had a potassium/sodium molar ratio of 1:2;
the preparation method of the extractant comprises the following steps:
(b1) The following raw materials by weight are taken: 13g of porous alumina, 6g of tetraglyme, 14g of propylene carbonate and 25g of sodium hydroxide solution;
(b2) Mixing tetraglyme and propylene carbonate to obtain a mixed solvent;
(b3) Mixing porous alumina and sodium hydroxide solution, stirring at 45deg.C for 35min, adding mixed solvent, and stirring to obtain extractant.
Example 3
A method for dearomatizing heavy pyrolysis gasoline and producing white oil, comprising the following steps:
(1) Pretreatment: the modified doping type RE-USY molecular sieve is used as a promoting catalyst, and the mass ratio is 0.32:1, adding the mixture into a heavy pyrolysis gasoline raw material, and controlling the volume space velocity to be 3h at the temperature of 240 ℃ under 0.8MPa -1 Carrying out pretreatment reaction to obtain an aromatic hydrocarbon crude product;
(2) Extraction: the mass ratio is 1:0.1, adding an extractant into the aromatic crude product, extracting for 7min at 82 ℃, wherein the reflux ratio is 1.2:1, respectively obtaining an aromatic-rich product and a non-aromatic product;
(3) And (3) a finished product: taking a non-aromatic hydrocarbon product, carrying out liquid phase reaction, and carrying out gas-liquid separation to obtain crude white oil;
the preparation method of the promotion catalyst comprises the following steps:
(a1) The following raw materials by weight are taken: 28g of RE-USY molecular sieve, 60g of sodium carbide aluminate solution, 22g of metal oxide and 9g of binder;
(a2) Adding RE-USY molecular sieve into sodium carbide aluminate solution, regulating pH value to 6.8, reacting at 65 ℃ for 2 hours, filtering and drying to obtain modified RE-USY molecular sieve;
(a3) Mixing the metal oxide precursor solution with a binder, stirring for 5 hours, adding a modified RE-USY molecular sieve, drying, and roasting at 350 ℃ for 6 hours to obtain a modified K/Na doped RE-USY molecular sieve;
wherein the binder is polyvinyl acetate emulsion; the metal oxide consists of potassium oxide and sodium oxide; the metal oxide precursor solution had a potassium/sodium molar ratio of 1:2;
the preparation method of the extractant comprises the following steps:
(b1) The following raw materials by weight are taken: 13g of porous alumina, 6g of tetraglyme, 14g of propylene carbonate and 25g of sodium hydroxide solution;
(b2) Mixing tetraglyme and propylene carbonate to obtain a mixed solvent;
(b3) Mixing porous alumina and sodium hydroxide solution, stirring at 45deg.C for 35min, adding mixed solvent, and stirring to obtain extractant.
Example 4
The same method for dearomatization of heavy pyrolysis gasoline and production of white oil according to example 3 is different in the preparation method of the promotion catalyst and the extractant, and the specific steps are as follows:
the preparation method of the promotion catalyst comprises the following steps:
(a1) The following raw materials by weight are taken: 33g of RE-USY molecular sieve, 70g of sodium carbide aluminate solution, 28g of metal oxide and 12g of binder;
(a2) Adding RE-USY molecular sieve into sodium carbide aluminate solution, regulating pH value to 6.5, reacting at 65 ℃ for 2 hours, filtering and drying to obtain modified RE-USY molecular sieve;
(a3) Mixing the metal oxide precursor solution with a binder, stirring for 5 hours, adding a modified RE-USY molecular sieve, drying, and roasting at 350 ℃ for 6 hours to obtain a modified K/Na doped RE-USY molecular sieve;
wherein the binder is polyvinyl acetate emulsion; the metal oxide consists of potassium oxide and sodium oxide; the metal oxide precursor solution had a potassium/sodium molar ratio of 1:3, a step of;
the preparation method of the extractant comprises the following steps:
(b1) The following raw materials by weight are taken: 16g of porous alumina, 9g of tetraglyme, 18g of propylene carbonate and 30g of sodium hydroxide solution;
(b2) Mixing tetraglyme and propylene carbonate to obtain a mixed solvent;
(b3) Mixing porous alumina and sodium hydroxide solution, stirring at 45deg.C for 35min, adding mixed solvent, and stirring to obtain extractant.
Comparative example 1
The process for dearomatization of heavy pyrolysis gasoline to produce white oil according to example 3 is different in that the RE-USY molecular sieve for preparing the catalyst promoter is replaced with HZSM-5 molecular sieve, and the rest of the steps are the same as in example 3.
Comparative example 2
The process for dearomatization of heavy pyrolysis gasoline to produce white oil according to example 3 is distinguished in that in step (1), the mass ratio of the pretreated heavy pyrolysis gasoline to the promoting catalyst is 1:0.55; the rest of the procedure is the same as in example 3.
Comparative example 3
The process for dearomatization of heavy pyrolysis gasoline to produce white oil according to example 3 differs in that in step (2), the reflux ratio of the extraction is 4:1, a step of; the rest of the procedure is the same as in example 3.
According to the dearomatization and white oil production methods of examples 1-4 and comparative examples 1-3, the purity, content and yield of the obtained products were calculated as shown in the following table:
as shown in the table above, the purity of the aromatic hydrocarbon-rich product obtained in example 3 reaches 97.3%, the chromaticity is 6.0, the liquefied gas yield is 22.5%, and the sulfur content of the crude white oil is 0.16wt%, which indicates that the invention can obtain the aromatic hydrocarbon-rich product with high purity and better chromaticity by respectively controlling the condition parameters of pretreatment reaction and extraction process, reasonably preparing and promoting catalyst and extractant, and preferably the dosage of the catalyst and extractant, through pretreatment, dearomatization, extraction and liquid phase reaction of the heavy pyrolysis gasoline raw material, and further improves the utilization value of the heavy pyrolysis gasoline.
The comparative example 1 adjusts the raw materials of the promoting catalyst, the chromaticity is improved to some extent, and different types of promoting catalysts influence the aromatic saturation activity, so that the invention adopts the RE-USY molecular sieve, the sodium carbide aluminate solution, the metal oxide and the modified doped RE-USY molecular sieve prepared by the binder as the promoting catalyst, can realize the reactions of rapid desulfurization, dearomatization and the like at a lower temperature, promote the decomposition of impurities such as sulfide, nitride and the like, avoid the aggravation cracking reaction, avoid the occurrence of the phenomenon of accelerating coking, further stabilize the subsequent extraction process, facilitate the separation of components, further obtain the aromatic-rich product with low chromaticity and the crude white oil with low sulfur content, and improve the purity of the aromatic-rich product; the comparative example 2 adjusts the dosage of the catalyst, the purity of the aromatic-rich product is reduced more, and when the ratio of the extractant to the catalyst to the raw materials is considered, the influence of the dosage of the catalyst on the subsequent extraction efficiency is also paid attention to, so that the purity of the aromatic-rich product is ensured by reasonably regulating and controlling the dosages of the catalyst and the extractant; the comparative example 3 adjusts the reflux ratio of extraction, the purity is slightly reduced, and the excessive reflux ratio reduces the selectivity of the aromatic hydrocarbon crude product to aromatic hydrocarbon, and simultaneously, the non-aromatic hydrocarbon component is easy to be excessively dissolved in the extractant, so that the back mixing phenomenon is caused.
Example 5
According to the method for dearomatization of heavy pyrolysis gasoline and production of white oil of example 3, the metal oxides potassium oxide and sodium oxide in the promoted catalyst were replaced with equal amounts of zinc oxide, and the purity of the aromatic-rich product was 94.1%.
Example 5 compared with example 3 shows that the invention can increase the selectivity of RE-USY molecular sieve to directionally convert light aromatic hydrocarbon and improve the stability of the promotion catalyst by adopting potassium oxide and sodium oxide to prepare the modified K/Na doped RE-USY molecular sieve.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. A method for dearomatizing heavy pyrolysis gasoline and producing white oil, which is characterized by comprising the following steps:
(1) Pretreatment: the modified doping type RE-USY molecular sieve is used as a promoting catalyst, and the mass ratio is 0.27-0.36:1, adding into heavy pyrolysis gasoline raw material, at 0.6-1.0MPa, 210-260 deg.C and volume space velocity of 2-5h -1 Carrying out pretreatment reaction to obtain crude areneA product;
(2) Extraction: the mass ratio is 1:0.08-0.12, adding extractant into the crude product of aromatic hydrocarbon, extracting for 6-8min at 74-86 ℃, and the reflux ratio is 0.5-2:1, respectively obtaining an aromatic-rich product and a non-aromatic product;
(3) And (3) a finished product: taking a non-aromatic hydrocarbon product, carrying out liquid phase reaction, and carrying out gas-liquid separation to obtain crude white oil;
the preparation method of the promotion catalyst comprises the following steps:
(a1) Weighing the following raw materials in parts by weight: 23-33 parts of RE-USY molecular sieve, 50-70 parts of sodium carbide aluminate solution, 16-28 parts of metal oxide and 7-12 parts of binder; the metal oxide consists of potassium oxide and sodium oxide;
(a2) Adding RE-USY molecular sieve into sodium carbide aluminate solution, regulating pH value to 6.5-6.9, reacting at 60-70 deg.C for 1-2h, filtering and stoving to obtain modified RE-USY molecular sieve;
(a3) Mixing the metal oxide precursor solution with a binder, stirring for 4-6h, adding a modified RE-USY molecular sieve, drying, and roasting for 5-8h at 300-400 ℃ to obtain a modified doped RE-USY molecular sieve;
the preparation method of the extractant comprises the following steps:
(b1) Weighing the following raw materials in parts by weight: 10-16 parts of porous alumina, 4-9 parts of tetraglyme, 12-18 parts of propylene carbonate and 20-30 parts of sodium hydroxide solution;
(b2) Mixing tetraglyme and propylene carbonate to obtain a mixed solvent;
(b3) Mixing porous alumina and sodium hydroxide solution, stirring at 40-50deg.C for 30-40min, adding mixed solvent, and stirring to obtain extractant.
2. A process for dearomatizing heavy pygas to produce white oil according to claim 1, wherein said binder is a polyvinyl acetate emulsion; the metal oxide precursor solution has a potassium/sodium molar ratio of 1:2-3.
3. A process for the dearomatization of heavy pyrolysis gasoline to produce white oil according to claim 1, characterized in that in step (a 2) the pH is adjusted to 6.7-6.8.
4. The process for dearomatization of heavy pyrolysis gasoline to produce white oil according to claim 1, wherein in the step (2), the extraction temperature is 82 ℃ and the extraction time is 7min.
5. The method for dearomatizing heavy pyrolysis gasoline to produce white oil according to claim 1, wherein in the step (2), the mass ratio of the aromatic crude product to the extractant is 1:0.1.
6. the method for dearomatization and production of white oil from heavy pyrolysis gasoline according to claim 1, wherein in the step (1), the pressure of the pretreatment reaction is 0.7-0.8MPa, and the temperature of the pretreatment reaction is 230-240 ℃.
7. The method for dearomatizing heavy pyrolysis gasoline to produce white oil according to claim 1, wherein in the step (1), the mass ratio of the promoting catalyst to the pretreated heavy pyrolysis gasoline is 0.32:1.
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| CN104511300A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurizing method |
| CN108329944A (en) * | 2018-02-08 | 2018-07-27 | 河北精致科技有限公司 | Utilize the method for catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products |
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| 劣质柴油非加氢精制技术;宦建波;《河南石油》;第17卷(第01期);第60-63页 * |
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