CN112876334B - Production device and preparation method of high-boiling-point aromatic solvent oil - Google Patents
Production device and preparation method of high-boiling-point aromatic solvent oil Download PDFInfo
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- CN112876334B CN112876334B CN202110055895.9A CN202110055895A CN112876334B CN 112876334 B CN112876334 B CN 112876334B CN 202110055895 A CN202110055895 A CN 202110055895A CN 112876334 B CN112876334 B CN 112876334B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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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
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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
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
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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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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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
- C10G2400/30—Aromatics
Abstract
The invention provides a preparation method of high-boiling-point aromatic solvent oil, which comprises the following steps: washing refinery dry gas with water to obtain washed dry gas; carrying out alkylation reaction on the water-washed dry gas and benzene, and rectifying and separating the obtained alkylation product to obtain a liquid-phase product and alkylation tail gas; rectifying and separating the liquid phase product to obtain benzene and heavy components; separating heavy components to obtain ethylbenzene and tower bottom materials; separating the tower bottom material to obtain high boiling point aromatic solvent oil and a material containing diethylbenzene; in the high boiling point aromatic hydrocarbon solvent oil, 10-50% of isopropyl benzene, 10-50% of n-propyl benzene, less than or equal to 15% of ethyl benzene, less than or equal to 30% of diethylbenzene and less than or equal to 0.1% of high boiling point substances are contained. The method comprises the steps of sequentially carrying out water washing and benzene alkylation on refinery dry gas, and then carrying out multiple separation to obtain high-boiling-point aromatic solvent oil and diethylbenzene. The process is simple, the refinery dry gas can be prepared into the high-boiling-point aromatic solvent oil, and the quality index of the high-boiling-point aromatic solvent oil meets the SA-1000 national standard.
Description
Technical Field
The invention belongs to the technical field of chemical equipment, and particularly relates to a production device of high-boiling-point aromatic solvent oil and a preparation method thereof.
Background
The device for preparing ethylbenzene from refinery dry gas utilizes the alkylation reaction of ethylene and benzene in the refinery dry gas to generate ethylbenzene, and propylbenzene is generated in the alkylation reaction process because the dry gas contains 0.05-1% of propylene. The generated impurities such as propyl benzene are separated in a subsequent rectifying tower, and the oil blending treatment is usually carried out, so that the generation value is low.
At present, the domestic production of the high-boiling-point aromatic hydrocarbon solvent oil mainly uses C10 heavy aromatic hydrocarbons as raw materials to produce the high-boiling-point aromatic hydrocarbon solvent oil. The distillation range of the process output 1#, 2#, and 3# high boiling point aromatic hydrocarbon solvent oil with the temperature of 170-198 ℃, 180-210 ℃, 210-260 ℃ respectively.
The process does not directly separate aromatic hydrocarbon products, so that the supply capacity of heavy materials for producing the high-boiling-point aromatic hydrocarbon solvent oil is insufficient, and the development of downstream aromatic hydrocarbon solvent oil is limited.
Disclosure of Invention
In view of the above, the present invention aims to provide a production apparatus for high boiling point aromatic hydrocarbon solvent oil and a preparation method thereof, wherein the method is simple and can prepare high boiling point aromatic hydrocarbon solvent oil.
The invention provides a preparation method of high-boiling-point aromatic solvent oil, which comprises the following steps:
washing refinery dry gas with water to obtain washed dry gas;
carrying out alkylation reaction on the water-washing dry gas and benzene to obtain an alkylation product;
rectifying and separating the alkylated product to obtain a liquid-phase product and an alkylated tail gas;
rectifying and separating the liquid phase product to obtain benzene and heavy components;
separating the heavy components to obtain ethylbenzene and a tower bottom material;
separating the tower bottom materials to obtain high-boiling-point aromatic solvent oil and a material containing diethylbenzene;
in the high-boiling-point aromatic hydrocarbon solvent oil, 10-50 vol% of isopropyl benzene, 10-50 vol% of n-propyl benzene, less than or equal to 15vol% of ethyl benzene, less than or equal to 30vol% of diethylbenzene and less than or equal to 0.1vol% of high-boiling-point substances are contained.
Preferably, the refinery dry gas contains 20-40 vol% of hydrogen, 20-60 vol% of methane, 5-20 vol% of ethane, 8-30 vol% of ethylene and 0.2-0.6 vol% of propylene;
the material at the bottom of the tower comprises 0-20 vol% of ethylbenzene, 5-25 vol% of cumene, 5-25 vol% of n-propyl benzene, 30-80 vol% of diethylbenzene and 0-5 vol% of high-boiling residues.
Preferably, the pressure of the alkylation reaction is 0.6-1 MPa, and the temperature is 320-380 ℃.
Preferably, the pressure for rectifying and separating the alkylation product is 0.4-0.7 MPa.
Preferably, when the liquid phase product is rectified and separated, the pressure at the top of the tower is 1.2-1.6 MPa, and the temperature at the bottom of the tower is 270-285 ℃.
Preferably, when the heavy components are separated, the pressure at the top of the tower is 80-120 KPa, and the temperature at the bottom of the tower is 205-220 ℃.
Preferably, when the tower bottom material is separated, the temperature of the tower bottom is 195-215 ℃, and the pressure of the tower top is 70-90 Kpa.
Preferably, when the heavy components are separated, the temperature at the bottom of the tower is 270-285 ℃, and the pressure at the top of the tower is 1.2-1.6 MPa.
The invention provides a production device of high-boiling-point aromatic solvent oil, which comprises a water washing tower, wherein a refinery gas inlet and a water washing dry gas outlet are formed in the water washing tower;
the reactor is connected with a water washing dry gas outlet of the water washing tower and is provided with a benzene inlet and an alkylation product outlet;
the crude separation tower is connected with an alkylation product outlet of the reactor, and a liquid-phase product outlet and an alkylation tail gas outlet are formed in the crude separation tower;
the benzene tower is connected with a liquid phase product outlet of the crude separation tower and is provided with a benzene outlet and a heavy component outlet;
the ethylbenzene tower is connected with a heavy component outlet of the benzene tower, and an ethylbenzene outlet and a tower bottom material outlet are formed in the ethylbenzene tower;
the solvent oil tower is connected with a tower bottom material outlet of the ethylbenzene tower;
a diethylbenzene tower and a high boiling point aromatic hydrocarbon solvent oil extraction unit which are respectively connected with the solvent oil tower.
Preferably, the high boiling point aromatic hydrocarbon solvent oil extraction unit comprises a steam generator connected with the overhead material outlet of the solvent oil tower;
a reflux drum connected to the steam generator;
a return pipe connected with the return tank and a high boiling point aromatic hydrocarbon solvent oil external delivery pipe.
The invention provides a preparation method of high-boiling-point aromatic solvent oil, which comprises the following steps: washing refinery dry gas with water to obtain washed dry gas; carrying out alkylation reaction on the water-washed dry gas and benzene to obtain an alkylation product; rectifying and separating the alkylation product to obtain a liquid-phase product and an alkylation tail gas; rectifying and separating the liquid phase product to obtain benzene and heavy components; separating the heavy components to obtain ethylbenzene and a tower bottom material; separating the tower bottom materials to obtain high-boiling-point aromatic solvent oil and a material containing diethylbenzene; in the high-boiling-point aromatic hydrocarbon solvent oil, 10-50 vol% of isopropyl benzene, 10-50 vol% of n-propyl benzene, less than or equal to 15vol% of ethyl benzene, less than or equal to 30vol% of diethylbenzene and less than or equal to 0.1vol% of high-boiling-point substances are contained. The method provided by the invention sequentially carries out water washing and benzene alkylation reaction on the refinery dry gas, and then obtains the high-boiling-point aromatic solvent oil and diethylbenzene through multiple separation. The process is simple, the refinery dry gas can be prepared into the high-boiling-point aromatic solvent oil, and the quality index of the high-boiling-point aromatic solvent oil meets the SA-1000 national standard.
Drawings
FIG. 1 is a schematic view of the apparatus and process for producing high-boiling-point aromatic hydrocarbon solvent oil according to the present invention.
Detailed Description
The invention provides a preparation method of high-boiling-point aromatic solvent oil, which comprises the following steps:
washing refinery dry gas with water to obtain washed dry gas;
carrying out alkylation reaction on the water-washed dry gas and benzene to obtain an alkylation product;
rectifying and separating the alkylated product to obtain a liquid-phase product and an alkylated tail gas;
rectifying and separating the liquid phase product to obtain benzene and heavy components;
separating the heavy components to obtain ethylbenzene and a tower bottom material;
separating the tower bottom materials to obtain high-boiling-point aromatic solvent oil and diethylbenzene;
in the high-boiling-point aromatic hydrocarbon solvent oil, 10-50 vol% of isopropyl benzene, 10-50 vol% of n-propyl benzene, less than or equal to 15vol% of ethyl benzene, less than or equal to 30vol% of diethylbenzene and less than or equal to 0.1vol% of high-boiling-point substances are contained.
The method provided by the invention sequentially carries out water washing and benzene alkylation reactions on the refinery dry gas, and then obtains the high-boiling-point aromatic solvent oil and diethylbenzene through multiple separations. The process is simple, the refinery dry gas can be prepared into the high-boiling-point aromatic solvent oil, and the quality index of the high-boiling-point aromatic solvent oil meets the SA-1000 national standard.
The invention washes the refinery dry gas to obtain the washed dry gas. In the invention, the water washing is performed by using desalted water; the desalted water is finished water obtained after impurities in water such as suspended matters, colloids, inorganic cations and anions are removed, and the impurity content is low; the pH value of the desalted water is 6-7, the chloride ion is less than or equal to 1mg/L, the hardness is less than or equal to 3, and the total salt is less than 800mg/L. The water washing can remove alkaline substances in the refinery dry gas; alkaline substances in the refinery dry gas mainly comprise ammonia gas, desulfurizer ethanolamine and the like; the water wash prevents the entry of alkaline species into the reactor which can lead to catalyst deactivation. The water washing is carried out in a water washing tower; in the water washing process, the water washing tower continuously supplements demineralized water, and sewage is continuously dropped from the bottom of the water washing tower and discharged; the water washing tower also carries out demineralized water reflux, so that alkaline substances in the dry gas can be reduced to be below 10 ppm; when the content of the alkaline substance is high, the alkaline substance can be effectively removed by increasing the supplementing amount of the demineralized water and increasing the reflux amount.
The process provided by the invention has no strict requirements on the components of the refinery dry gas, has high operation flexibility and easily obtained raw materials; the project investment during the pretreatment of the raw materials can be reduced, and the device cost is saved. In the invention, the refinery dry gas contains 11-40 vol% of hydrogen, 20-60 vol% of methane, 5-20 vol% of ethane, 8-30 vol% of ethylene and 0.2-1.2 vol% of propylene. The refinery dry gas also comprises 0.1-1.5% of propane, 5-8% of oxygen, 15-25 vol% of nitrogen, 1.3-1.5 vol% of CO and CO 2 0.1 to 0.3 percent. If the ethylene content in the gas rises and the propylene and the components above C3 are reduced, the ethylbenzene content in the alkylation product is increased, the propylbenzene content is reduced, so that the ethylbenzene yield of the device is increased, the propylbenzene yield and the like are reduced, the components in the feed of the solvent oil tower are heavier, and the distillation range of the high-boiling-point aromatic hydrocarbon solvent oil is increased.
After the water washing dry gas is obtained, the invention carries out alkylation reaction on the water washing dry gas and benzene to obtain an alkylation product. The alkylation reaction is carried out in a reactor; the dry gas from the water washing is preferably divided into N streams which enter the reactor from the side of the reactor. Benzene enters the reactor from the top of the reactor. The pressure of the alkylation reaction is preferably 0.6-1.0 MPa; the reaction temperature is preferably 320-380 ℃; in a specific embodiment, the temperature of the alkylation reaction is 355-360 ℃. The benzene enters a benzene reactor in a heated state, and the temperature of the benzene is 375-385 ℃; the flow rate of the benzene is 36 to 42t/h.
The alkylation product, namely the alkylation product, enters a coarse separation tower for rectification separation to obtain a liquid phase product and an alkylation tail gas. The pressure for rectifying and separating the alkylation product is preferably 0.4-0.7 MPa, and more preferably 0.5-0.7 MPa; in the specific embodiment, the pressure for rectifying and separating the alkylation product is 0.55MPa; the temperature at the top of the crude separation column is preferably 90 to 120 ℃ and preferably 115 to 120 ℃. The material at the tower top is cooled to below 45 ℃ by air cooling, at the moment, the benzene is liquefied and changed into a liquid phase which is left in a reflux tank to be used as the reflux of a coarse separation tower, the gas phase is the alkylation tail gas, the alkylation tail gas is unreacted alkane, and the alkylation tail gas can be sent out to a gas pipe network; the liquid phase product is conveyed to the bottom of the tower to participate in the next rectification separation process.
The liquid phase product is conveyed from the bottom of the rough separation tower to the next rectification separation process, namely the liquid phase product enters the benzene tower for rectification separation. The invention has higher requirements on the benzene tower, benzene in the liquid phase product needs to be completely separated from the top of the tower, and the bottom of the tower is provided with the heavy component products such as ethylbenzene, propylbenzene and the like. The tower diameter of the benzene tower is 2000-2500 mm; 100 layers of trays are arranged in the benzene tower, and the plate spacing of the trays is 450-500 mm; the pressure drop of the whole tower is controlled within 120 KPa. The main parameters of the benzene column are shown in table 1:
TABLE 1 main parameters of the benzene column
The feeding position of the benzene tower is between 30 and 40 layers of tower trays, the benzene tower is fed in three strands, and the side pumping of the benzene tower is arranged on 96 layers; temperature monitoring points are respectively arranged on the 10 layers, the 20 layers, the 80 layers and the 90 layers, the tower top and the tower bottom, and the temperature change is required to be monitored during normal operation; the treatment capacity of the benzene tower is 15-50 t/h.
In the invention, when the benzene tower is normally operated, the pressure at the top of the tower is 0.2-1.6 MPa, and the temperature at the bottom of the tower is 270-285 ℃; in the concrete embodiment, the pressure at the top of the tower is 1.5-1.6 Mpa, and the temperature at the bottom of the tower is controlled at 280-282 ℃. In order to prevent the benzene tower from rushing, namely, materials at the bottom of the tower come to the upper part of the tower, a benzene reflux device is arranged at the top of the benzene tower; the reflux temperature is 140-160 ℃. The reflux temperature may be controlled by a steam generator. In the invention, the temperature of the 10 th layer of tray in the benzene tower is 270-280 ℃; the temperature of the tray at the 20 th layer is lower than that of the tray at the 10 th layer; the temperature of the tray at the 20 th layer and the temperature of the tray at the 10 th layer are controlled within 10 ℃. The temperature of 80 th and 90 th trays is 195-205 ℃; the temperature difference between the 80 th and 90 th trays was controlled at 2 ℃. The invention controls different temperature points of each section according to different boiling points of each component. If the temperature difference between the 10 th layer and the 20 th layer is more than or equal to 10 ℃, the benzene in the benzene tower is more, and the benzene is more extracted from the side extraction part of the benzene tower; when the temperature difference is less than 10 ℃, the side benzene extraction amount is reduced. If the difference between the temperatures of the 80 th and 90 th layers is large, indicating upward migration of heavies, then the difference between the temperatures of the 80 th and 90 th layers can be reduced by lowering the reflux temperature. Through the operation, the benzene content at the bottom of the benzene tower can be controlled within 0.01 percent, and the purity of the benzene extracted from the tower top is controlled to be more than 99.6 percent.
And the tower bottom material separated in the benzene tower, namely the heavy component, enters an ethylbenzene tower to be separated, so that ethylbenzene and the tower bottom material are obtained. Ethylbenzene is separated from the top of the tower, and other heavy components are taken as a bottom material and conveyed to the solvent oil tower from the bottom of the tower for separation. In the invention, when the tower bottom material is separated in the ethylbenzene tower, the pressure at the top of the tower is 80-120 KPa, and the temperature at the bottom of the tower is 205-220 ℃. In the concrete embodiment, when the ethylbenzene is separated in the ethylbenzene tower, the pressure at the top of the ethylbenzene tower is 100-115 KPa, the temperature at the bottom of the ethylbenzene tower is 210-215 ℃, and the reflux quantity of the ethylbenzene tower is controlled to be 28-32 t/h.
And separating the tower bottom materials to obtain high-boiling-point aromatic solvent oil and a material containing diethylbenzene. The material at the bottom of the tower comprises 0-20 vol% of ethylbenzene, 5-25 vol% of isopropyl benzene, 5-25 vol% of n-propyl benzene, 30-80 vol% of diethylbenzene and 0-5 vol% of high-boiling residues. Separating the tower bottom materials in a solvent oil tower; the solvent oil tower is a packed tower, and the packing is 250 regular packing; the tower diameter of the solvent oil tower is 1000mm; the total height of the filler is 30000mm, and the filler is divided into 6 sections. The treatment capacity of the solvent oil tower is 1-10 t/h.
The temperature of the tower bottom of the solvent oil tower is preferably 195-215 ℃, the temperature is adjusted by the quantity of heat-conducting oil of a reboiler at the tower bottom, and the temperature of the tower bottom is more preferably 210-215 ℃; the pressure at the column top is preferably 70 to 90KPa, more preferably 80 to 90KPa. The tower top is provided with a reflux unit, the reflux unit comprises a reflux tank and a steam generator, and the pressure of the tower top is adjusted by controlling the pressure of the reflux tank; the temperature at the top of the tower is preferably 165-185 ℃, and the temperature at the top of the tower is adjusted by the reflux quantity and the reflux temperature; the temperature at the top of the column is more preferably 180 to 185 ℃. The temperature of the material at the top of the tower is 130-145 ℃ after passing through a steam generator in a reflux unit; this temperature is regulated by the steam production of the steam generator. A part of the tower top material passing through the steam generator, namely the high boiling point aromatic hydrocarbon solvent oil, flows back to the solvent oil tower, and the rest part is extracted and sent out; the volume ratio of the reflux amount to the extraction amount of the high-boiling-point aromatic hydrocarbon solvent oil is 1; in the specific embodiment, the volume ratio of the reflux amount to the extracted amount of the high-boiling-point aromatic hydrocarbon solvent oil is preferably 1.
In the invention, an on-line analyzer is arranged at the delivery position of the high-boiling-point aromatic solvent oil; in the high-boiling-point aromatic hydrocarbon solvent oil, 10-50 vol% of isopropyl benzene, 10-50 vol% of n-propyl benzene, less than or equal to 15vol% of ethyl benzene, less than or equal to 30vol% of diethyl benzene and less than or equal to 0.1vol% of high-boiling-point substances are contained. The ethylbenzene content in the high-boiling-point aromatic solvent oil is controlled to be less than or equal to 15%, so that the initial boiling point of the high-boiling-point aromatic solvent oil is ensured; the ethylbenzene content can be controlled by increasing the temperature at the bottom of the ethylbenzene tower and reducing the ethylbenzene content in the ethylbenzene tower; the diethylbenzene content is less than or equal to 30 percent, and the dry point temperature of the high-boiling-point aromatic solvent oil is 176-178 ℃; the content of high-boiling residues is controlled to be below 0.1 percent, and the high-boiling residues can be controlled by increasing the reflux quantity and reducing the temperature of the tower bottom; the high boiling point substance content can cause the coating film to be rough and cracked in the later stage of film forming because of the tailings in the distillation process in the baking type coating, thereby affecting the performance, and therefore, the high boiling point substance content needs to be strictly controlled. And (3) continuously delivering the high-boiling-point aromatic hydrocarbon solvent oil to the outside through an online analyzer, and if the distillation range of the solvent oil is higher, reducing the temperature at the bottom of the ethylbenzene tower and increasing the reflux quantity of the ethylbenzene tower, so that the ethylbenzene content at the bottom of the ethylbenzene tower is increased, the distillation range of the solvent oil is reduced, and vice versa.
The material at the bottom of the solvent oil tower, namely the material containing diethylbenzene, is conveyed to a diethylbenzene tower, diethylbenzene is separated from the top of the diethylbenzene tower and can be sold as a product, and the high-boiling residue at the bottom of the solvent oil tower can be used for blending diesel oil. The diethylbenzene tower is a negative pressure tower, the pressure of the tower top is-30 Kpa to-50 Kpa, and the temperature of the tower bottom is 190-210 ℃; in the specific embodiment, the pressure at the top of the tower is-45 Kpa to-50 Kpa, and the temperature at the bottom of the tower is 200-210 ℃.
The content of aromatic hydrocarbon in the high-boiling-point aromatic hydrocarbon solvent produced by the process is over 99 percent, and the high-boiling-point aromatic hydrocarbon solvent has good solubility. Does not contain triphenyl, has small pungent smell and is environment-friendly. The product has the characteristics of proper distillation range and volatility, strong dissolving power, low odor and the like, is widely applied to the industries of paint, printing ink, pesticide, plastics and the like, particularly baking type coatings, exerts high dissolving power in the later stage of film forming, enables a coating film to be flat and less in orange peel, and has no residual tailings in the distillation range, so that the performance of the coating film cannot be influenced by being left in the coating film for a long time; the bromine number is low, and the performances of resin and active pigment in the coating are not influenced; it has very high flash point, low toxicity and high safety. In addition, the use of the compound in paint and pesticide can avoid the harm of triphenyl to the environment.
The invention provides a production device of high-boiling-point aromatic solvent oil, which comprises a water washing tower, wherein a refinery gas inlet and a water washing dry gas outlet are formed in the water washing tower;
the reactor is connected with a water washing dry gas outlet of the water washing tower and is provided with a benzene inlet and an alkylation product outlet;
the crude separation tower is connected with an alkylation product outlet of the reactor, and a liquid-phase product outlet and an alkylation tail gas outlet are formed in the crude separation tower;
the benzene tower is connected with a liquid phase product outlet of the crude separation tower and is provided with a benzene outlet and a heavy component outlet;
the ethylbenzene tower is connected with a heavy component outlet of the benzene tower, and an ethylbenzene outlet and a tower bottom material outlet are formed in the ethylbenzene tower;
the solvent oil tower is connected with a tower bottom material outlet of the ethylbenzene tower;
a diethylbenzene tower and a high boiling point aromatic hydrocarbon solvent oil extraction unit which are respectively connected with the solvent oil tower.
In the invention, a benzene reflux device is preferably arranged at the top of the benzene tower; the benzene reflux device comprises a steam generator, a reflux pipe and a reflux pump which are connected with a reflux benzene outlet at the top of the benzene tower; the benzene treated by the benzene reflux device enters the benzene tower through a reflux benzene inlet.
The high boiling point aromatic hydrocarbon solvent oil extraction unit comprises a steam generator connected with a material outlet at the top of the solvent oil tower;
a reflux drum connected to the steam generator;
a return pipe connected with the return tank and a high boiling point aromatic hydrocarbon solvent oil external delivery pipe.
And an online analyzer is arranged on the high-boiling-point aromatic hydrocarbon solvent oil delivery pipeline and is used for carrying out component analysis on the delivered high-boiling-point aromatic hydrocarbon solvent oil.
The invention tests the quality index parameters of the high boiling point aromatic solvent oil, and the results are shown in the table 1:
TABLE 1 quality index parameters of high boiling point aromatic solvent oil of the process index provided by the present invention
In order to further illustrate the present invention, the following will describe in detail a production apparatus of a high boiling point aromatic hydrocarbon solvent oil and a preparation method thereof, which are provided by the present invention, with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The device amount of the ethylbenzene is 10t/h based on the dry gas in the refinery, the ethylene content in the dry gas in the refinery is 17.5vol%, the propylene content is 1.2vol%, the methane content is 26vol%, the ethane content is 15vol%, the propane content is 1.5vol%, the nitrogen content is 25vol%, the hydrogen content is 11vol%, the carbon monoxide content is 1.5vol%, the components above C3 are 1.3vol%, the dry gas enters a washing tower for washing, the washing tower is replenished with water for 1.5t/h, the washing water circulation amount is 25t/h, the dry gas after washing to remove alkaline substances enters a reactor, the dry gas enters the reactor from the side surface in three branches, hot benzene (380 ℃) enters from the top of the reactor, the hot benzene content is controlled to be 36-40 t/h, the alkylation reaction temperature in the reactor is 355-360 ℃, the alkylation reaction product enters a crude separation tower for separation, the rectification separation pressure of the alkylation product is 0.55MPa, the temperature in the top of the crude separation tower is 115-120 ℃, the materials at the top of the tower are cooled to be below 45 ℃, the benzene is liquefied into a liquid phase and is left in a reflux tank for use, and the gas phase is the alkylation tower for reflux. The alkylation tail gas is unreacted alkane, and the alkylation tail gas can be sent to a gas pipe network; the liquid phase at the bottom of the crude separation tower enters a benzene tower, the pressure of the benzene tower is controlled to be 1.5Mpa, the temperature at the bottom of the benzene tower is controlled to be 280 ℃, and the side benzene extraction amount of the benzene tower is 30t/h. And the tower bottom material separated in the benzene tower, namely the heavy component, enters an ethylbenzene tower for separation to obtain ethylbenzene and the tower bottom material. And the benzene tower bottom material enters an ethylbenzene tower, ethylbenzene is separated from the tower top, and other heavy components are taken as tower bottom materials and conveyed to a solvent oil tower from the tower bottom for separation. When the tower bottom materials are separated in the ethylbenzene tower, the pressure at the top of the tower is 100-115 KPa, the temperature at the bottom of the tower is 210-215 ℃, the reflux quantity of the ethylbenzene tower is controlled to be 28-32 t/h, ethylbenzene is separated from the tower top, the extraction quantity of the ethylbenzene is 8t/h, and the tower bottom materials enter the solvent oil tower. The temperature of the bottom of the solvent oil tower is 210-215 ℃, the pressure of the top of the solvent oil tower is 80-90 KPa, the temperature of the top of the solvent oil tower is 180-185 ℃, and the temperature of the top of the solvent oil tower is adjusted by reflux quantity and reflux temperature. The temperature of the material at the top of the tower is 135-145 ℃ after passing through a steam generator in a reflux unit; this temperature is regulated by the steam production of the steam generator. A part of the tower top material passing through the steam generator, namely the high-boiling-point aromatic hydrocarbon solvent oil, flows back to the solvent oil tower, and the rest is extracted and sent out; the volume ratio of the reflux amount to the extraction amount of the high-boiling-point aromatic hydrocarbon solvent oil is 1. The material at the bottom of the solvent oil tower is sent to a diethylbenzene tower, the diethylbenzene is separated from the top of the diethylbenzene tower by the diethylbenzene tower, the diethylbenzene content is 400kg/h, and the high-boiling-point material at the bottom of the solvent oil tower is 200kg/h. The diethyl benzene tower is a negative pressure tower, the pressure of the top of the tower is-45 kpa to-50 kpa, and the temperature of the bottom of the tower is 200 ℃ to 210 ℃.
In this example, a sample of the collected high boiling point solvent oil was randomly sampled and examined, and the results showed that the high boiling point solvent oil contained 39.6% cumene, 32.3% n-propylbenzene, 12.5% ethylbenzene, 12.8% diethylbenzene, 0.1% high boiling point components and 2.7% other components.
The high-boiling point solvent oil has the initial boiling point of 152 ℃, the 10 percent evaporation temperature of 156 ℃, the 90 percent evaporation temperature of 170 ℃, the dry point of 176 ℃ and the density of 0.871g/cm 3 The aromatic hydrocarbon content is 98.6vol%, the flash point is 44.5 ℃, and the index requirement is met.
The yield of the high boiling point solvent oil is 4-6%.
Example 2
The method comprises the steps of feeding 10t/h of ethylbenzene device by using the amount of dry gas in a refinery, feeding 18.5vol% of ethylene, 0.7vol% of propylene, 26vol% of methane, 15vol% of ethane, 1.5vol% of propane, 25vol% of nitrogen, 11vol% of hydrogen, 1.5vol% of carbon monoxide and 0.8vol% of components above C3 in the dry gas in the refinery, feeding the dry gas into a washing tower for washing, supplementing water by the washing tower for 1.5t/h, and feeding the dry gas with 25t/h of washing water circulation amount, removing alkaline substances after washing into a reactor, feeding the dry gas into the reactor from the side, feeding hot benzene (380 ℃) from the top of the reactor, controlling the hot benzene amount to be 38-42 t/h (increasing the ethylene content in the dry gas, correspondingly increasing the circulating benzene amount, and ensuring full reaction of olefin), feeding the alkylation reaction product into a crude fractionating tower for separation at an alkylation reaction temperature of 355-360 ℃ in the reactor, feeding the alkylation product into a crude fractionating tower for separation, wherein the separation pressure of the refined alkylation product is 0.55MPa, the temperature of the crude tower is 115-120 ℃, cooling the crude benzene material to be below 45 ℃, and the crude benzene is changed into a liquefied gas phase reflux tank, and the reflux is used as tail gas phase reflux. The alkylation tail gas is unreacted alkane, and the alkylation tail gas can be sent to a gas pipe network; the liquid phase at the bottom of the rough separation tower enters a benzene tower, the pressure of the benzene tower is controlled to be 1.5-1.6 Mpa, the temperature at the bottom of the benzene tower is controlled to be 280-282 ℃ (ethylbenzene in the alkylation product is increased, ethylbenzene in the feeding of the benzene tower is increased, the pressure is improved, and the separation is convenient), and the side benzene extraction amount of the benzene tower is 28-30 t/h. And the tower bottom material separated in the benzene tower, namely the heavy component, enters an ethylbenzene tower for separation to obtain ethylbenzene and the tower bottom material. And the benzene tower bottom material enters an ethylbenzene tower, ethylbenzene is separated from the tower top, and other heavy components are taken as tower bottom materials and conveyed to a solvent oil tower from the tower bottom for separation. In the invention, when the tower bottom material is separated in an ethylbenzene tower, the pressure at the top of the tower is 105-115 KPa, the temperature at the bottom of the tower is 205-210 ℃, the reflux quantity of the ethylbenzene tower is controlled at 30-35 t/h (the temperature at the bottom of the ethylbenzene tower is properly reduced, and the content of ethylbenzene at the bottom of the ethylbenzene tower is increased, so that the distillation range of high-boiling-point aromatic hydrocarbon solvent oil is reduced), the ethylbenzene is separated at the top of the tower, the extraction quantity of the ethylbenzene is 8t/h, and the tower bottom material enters the solvent oil tower. The temperature of the bottom of the solvent oil tower is 210-215 ℃, the pressure of the top of the solvent oil tower is 80-90 KPa, the temperature of the top of the solvent oil tower is 180-185 ℃, and the temperature of the top of the solvent oil tower is adjusted by reflux quantity and reflux temperature. The temperature of the material at the top of the tower is 135-145 ℃ after passing through a steam generator in a reflux unit; this temperature is regulated by the steam production of the steam generator. A part of the tower top material passing through the steam generator, namely the high boiling point aromatic hydrocarbon solvent oil, flows back to the solvent oil tower, and the rest part is extracted and sent out; the volume ratio of the reflux amount to the extraction amount of the high-boiling-point aromatic hydrocarbon solvent oil is 1. The material at the bottom of the solvent oil tower is sent to a diethylbenzene tower, the diethylbenzene is separated from the top of the diethylbenzene tower by the diethylbenzene tower, the diethylbenzene content is 400kg/h, and the high-boiling-point material at the bottom of the solvent oil tower is 200kg/h. The diethyl benzene tower is a negative pressure tower, the pressure of the tower top is-45 Kpa to-50 Kpa, and the temperature of the tower bottom is 200-210 ℃.
In this example, a sample of the collected high boiling point solvent oil was randomly sampled and examined, and the results were 36.5% cumene, 33.5% n-propylbenzene, 14.3% ethylbenzene, 13.5% diethylbenzene, 0.03% high boiling point substance and 2.17% other components.
The high boiling point solvent oil has initial boiling point of 151.8 deg.C, 10% evaporation temperature of 155.5 deg.C, 90% evaporation temperature of 169.7 deg.C, dry point of 175.5 deg.C, and density of 0.869g/cm 3 The aromatic hydrocarbon content is 98.9vol%, the flash point is 43.8 ℃, and the index requirement is met.
The yield of the high boiling point solvent oil is 3.5-5.5%.
From the above examples, the present invention provides a method for preparing high boiling point aromatic hydrocarbon solvent oil, comprising the following steps: washing refinery dry gas with water to obtain washed dry gas; carrying out alkylation reaction on the water-washing dry gas and benzene to obtain an alkylation product; rectifying and separating the alkylation product to obtain a liquid-phase product and an alkylation tail gas; rectifying and separating the liquid phase product to obtain benzene and heavy components; separating the heavy components to obtain ethylbenzene and a tower bottom material; separating the tower bottom materials to obtain high-boiling-point aromatic solvent oil and a material containing diethylbenzene; in the high-boiling-point aromatic hydrocarbon solvent oil, 10-50 vol% of isopropyl benzene, 10-50 vol% of n-propyl benzene, less than or equal to 15vol% of ethyl benzene, less than or equal to 30vol% of diethylbenzene and less than or equal to 0.1vol% of high-boiling-point substances are contained. The method provided by the invention sequentially carries out water washing and benzene alkylation reactions on the refinery dry gas, and then obtains the high-boiling-point aromatic solvent oil and diethylbenzene through multiple separations. The process is simple, the refinery dry gas can be prepared into the high-boiling-point aromatic solvent oil, and the quality index of the high-boiling-point aromatic solvent oil meets the SA-1000 national standard.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A preparation method of high-boiling-point aromatic solvent oil comprises the following steps:
washing refinery dry gas with water to obtain washed dry gas; 20 to 40vol% of hydrogen, 20 to 60vol% of methane, 5 to 20vol% of ethane, 8 to 30vol% of ethylene and 0.2 to 0.6vol% of propylene in the refinery dry gas;
carrying out alkylation reaction on the water-washed dry gas and benzene to obtain an alkylation product; the pressure of the alkylation reaction is 0.6 to 1MPa, and the temperature is 320 to 380 ℃;
rectifying and separating the alkylated product to obtain a liquid-phase product and an alkylated tail gas; the pressure for rectifying and separating the alkylation product is 0.4 to 0.7MPa; when the liquid phase product is rectified and separated, the pressure at the top of the tower is 1.2 to 1.6MPa, and the temperature at the bottom of the tower is 270 to 285 ℃;
rectifying and separating the liquid phase product to obtain benzene and heavy components;
separating the heavy components to obtain ethylbenzene and a tower bottom material; when the heavy components are separated, the pressure at the top of the tower is 80 to 120KPa, and the temperature at the bottom of the tower is 205 to 220 ℃; 0 to 20vol% of ethylbenzene, 5 to 25vol% of cumene, 5 to 25vol% of n-propylbenzene, 30 to 80vol% of diethylbenzene and 0 to 5vol% of high-boiling residues in the tower bottom material;
separating the tower bottom materials to obtain high-boiling-point aromatic solvent oil and a material containing diethylbenzene; when the materials at the bottom of the tower are separated, the temperature at the bottom of the tower ranges from 195 to 215 ℃, and the pressure at the top of the tower ranges from 70 to 90Kpa;
in the high-boiling-point aromatic hydrocarbon solvent oil, 10 to 50vol% of cumene, 10 to 50vol% of n-propylbenzene, less than or equal to 15vol% of ethylbenzene, less than or equal to 30vol% of diethylbenzene and less than or equal to 0.1vol% of high-boiling-point substances.
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