CN111592912A - Alkylation method and alkylation equipment - Google Patents

Alkylation method and alkylation equipment Download PDF

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Publication number
CN111592912A
CN111592912A CN202010481561.3A CN202010481561A CN111592912A CN 111592912 A CN111592912 A CN 111592912A CN 202010481561 A CN202010481561 A CN 202010481561A CN 111592912 A CN111592912 A CN 111592912A
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China
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alkylation
reactor
ionic liquid
rectifying tower
mixture
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陈锡武
陈鉴
解委托
薛建颢
代训达
刘玄
陈南
张媛
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Nanjing Kemisicui New Energy Technology Co ltd
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Nanjing Kemisicui New Energy Technology Co ltd
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • 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
    • C10G2400/02—Gasoline

Abstract

The invention discloses an alkylation method and alkylation equipment, wherein C4 alkane and C4 alkene are used as raw materials, and ionic liquid is used as a catalyst to carry out alkylation reaction in an alkylation reactor; and after the reaction, the components are settled and separated to obtain an alkylated crude product, the alkylated crude product enters a rectifying tower, wherein the liquefied gas component is discharged from the top of the rectifying tower, the mixture of the ionic liquid and the heavy component is discharged from the bottom of the rectifying tower and is conveyed to an alkylation reactor again, the gasoline component is conveyed to a hydrodechlorination reactor through a pipeline arranged at the side of the rectifying tower to be hydrogenated and then enters a dechlorination reactor, and the gasoline component is discharged after dechlorination by a dechlorinating agent in the dechlorination reactor. The invention does not adopt alkali washing and water washing processes, does not generate waste alkali and waste water, has small loss of ionic liquid, does not produce heavy components in products and has high utilization rate of hydrocarbons.

Description

Alkylation method and alkylation equipment
Technical Field
The invention relates to an alkylation method and alkylation equipment.
Background
With the rapid development of the automobile industry and the increasing attention of human beings on environmental protection, the demand of various countries in the world for lead-free gasoline with high octane number and low content of aromatic hydrocarbon and olefin is rapidly increasing. At present, adding an alkylate oil to gasoline becomes an effective method for maintaining high octane value and low vapor pressure of gasoline.
In the industrial production process of the alkylate oil, the catalyst adopted in the alkylation process of alkane and olefin is mainly strong acid liquid such as concentrated sulfuric acid or hydrofluoric acid, and the strong acid liquid has the problems of strong corrosivity, difficult production operation, complex post-treatment process of reaction products and the like, and also has the problem of serious environmental pollution.
As a novel compound system, the ionic liquid has the characteristics of environmental friendliness, low corrosivity, low toxicity, adjustable acidity and physicochemical properties, easiness in separation from products, high recycling and the like, so that the ionic liquid can be an ideal novel catalytic material for replacing liquid strong acids such as concentrated sulfuric acid, hydrofluoric acid and the like to catalyze the C4 alkylation reaction. In recent years, due to the advantages of ionic liquids as catalysts, research on the application of ionic liquids as catalysts to prepare alkylate oil is increasing.
For example, U.S. Pat. No. 5,7285698, Chinese patents CN1500764A, CN1432627A, CN102108306A, CN1907924A and CN101619010A each disclose various alkylation reaction processes using ionic liquid as catalyst, wherein the yield of the alkylate oil product prepared by some processes can reach 170-180% of the olefin feed, the proportion of C8 in the alkylate oil can reach 60-80%, and RON (research octane number) can reach 93-98.
However, compared with concentrated sulfuric acid, ionic liquids also have some disadvantages, such as their lower density, higher solubility with hydrocarbons and more difficult separation. In order to remove ionic liquid from alkylate, a method of washing with alkali and then with water is adopted in industry. A large amount of waste lye and waste water is produced, while part of the ionic liquid is lost.
Chinese patent CN106554808B provides a method for separating ionic liquid from alkylation reaction product, which can reduce the ionic liquid in crude alkylate oil to below 1% by two-stage cyclone separation. Chinese patent CN102639469B invented a method for preparing alkylate, in which the alkylate reaction product and ionic liquid are separated by two-stage cyclone separator, and the ionic liquid in alkylate can be reduced to below 0.5%. Chinese patent CN108795481A discloses a method and a device for purifying and separating hydrocarbon and catalyst in ionic liquid alkylation reaction effluent, which adopts a two-stage packed bed coalescer, wherein the first stage is vertical, the second stage is horizontal, and ionic liquid in an alkylation product can be reduced from 0.5% to 5-8 ppm.
Meanwhile, the inevitable water in the reaction raw materials can cause the hydrolysis of the aluminum trichloride to generate hydrogen chloride, the hydrogen chloride and the olefin are easy to generate chlorohydrocarbon, and if the hydrogen chloride is not removed, the engine of the automobile can be corroded.
Chinese patent CN204918487U provides an alkylate dechlorination device, which adopts two dechlorination tanks, can be connected in series or in parallel, so as to improve the efficiency of dechlorination agent. Chinese patent CN108636348A discloses an adsorbent loaded with alkali active components, which is an adsorbent loaded with alkali metal on a molecular sieve, and the adsorption dechlorination conditions are as follows: the temperature in the fixed bed reactor is 0-50 ℃, the pressure is 0.5-2.0MPa, and the space velocity of the ionic liquid alkylate is 0.25-4h-1(ii) a The regeneration conditions were: the temperature is 100 ℃ and 180 ℃, the pressure is 0.1-0.5MPa, and the space velocity of the steam is 30-1000h-1(ii) a The chlorine content of the alkylate can be reduced from 350ppm to about 1 ppm. Chinese patent CN102108306B discloses an alkylation reaction method using ionic liquid as a catalyst, which adopts a distillation and/or adsorption method to separate C3-C5 monosubstituted halogenated hydrocarbon, and then returns the halogenated hydrocarbon to an alkylation reactor to prolong the service life of the ionic liquid, and can improve the treatment efficiency from 50 g of raw material per gram of ionic liquid to 120 g of raw material per gram of ionic liquid, but does not relate to the removal of halogenated hydrocarbon with higher carbon number.
In order to remove ionic liquid from alkylate, a method of washing with alkali and then with water is adopted in industry. A large amount of waste lye and waste water are generated, and part of ionic liquid is lost, so that the cost is increased. Even though Chinese patents CN106554808B and CN102639469B can reduce the ionic liquid in the alkylate to below 1 percent or 0.5 percent, a large amount of alkali washing and water washing are still needed; although the Chinese patent CN108795481A can reduce the ionic liquid in the alkylate to 5-8ppm, and reduce the dosage of alkaline washing and water washing, a two-stage packed bed coalescer is added, and the packed bed coalescer is complex to manufacture and increases the cost. The alkylate is subjected to organic chloride removal through adsorption, the operation is complex, the alkylate loss is large, and meanwhile, the problem of how to utilize the desorbed organic chloride exists.
It can be seen that there is a need for improvement in at least one of the above-mentioned problems with the prior art.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide an alkylation method and an alkylation apparatus, which can eliminate the alkali washing and water washing processes in the existing ionic liquid alkylation process and is environment-friendly.
In order to achieve the above object, the present invention provides an alkylation method, which comprises carrying out alkylation reaction in an alkylation reactor by using C4 alkane and C4 alkene as raw materials and using ionic liquid as a catalyst; and after the reaction, the components are settled and separated to obtain an alkylated crude product, the alkylated crude product enters a rectifying tower, wherein the liquefied gas component is discharged from the top of the rectifying tower, the mixture of the ionic liquid and the heavy component is discharged from the bottom of the rectifying tower and is conveyed to an alkylation reactor again, the gasoline component is conveyed to a hydrodechlorination reactor through a pipeline arranged at the side of the rectifying tower to be hydrogenated and then enters a dechlorination reactor, and the gasoline component is discharged after dechlorination by a dechlorinating agent in the dechlorination reactor.
Preferably, the C4 olefin is selected from one or a mixture of 1-butene, 2-butene or isobutene; the C4 alkane is isobutane.
Preferably, the water or oxygenate content of the C4 alkane and the C4 alkene is less than 10 ppm.
Preferably, the anion of the ionic liquid is one or more than one metal chloride; the cation of the ionic liquid is one or more of hydrochloride of amine containing alkyl, hydrochloride of imidazole or hydrochloride of pyridine.
Preferably, the alkylation reaction conditions are: the molar ratio of the C4 alkane to the C4 alkene is 5: 1-40: 1, the reaction temperature is 0-50 ℃, and the reaction pressure is 0.1-1.0 Mpa.
Preferably, the reacted components after the alkylation reaction comprise reaction products and ionic liquid, the reacted components are discharged from the top of the alkylation reactor and enter a flash tank, and after C4 alkane is flashed, the liquid phase enters a settling separator for settling separation.
Preferably, after the alkylation crude product enters a primary rectifying tower, discharging liquefied gas from the top of the primary rectifying tower, discharging gasoline components from the side edge of the primary rectifying tower, and extracting a mixture of ionic liquid and heavy components from the bottom of the primary rectifying tower; or the alkylated crude product enters a secondary rectifying tower, liquefied gas is discharged from the top of the primary rectifying tower, and the mixture at the bottom of the tower enters the secondary rectifying tower; and discharging gasoline components from the top of the secondary rectifying tower, and extracting a mixture of ionic liquid and heavy components from the bottom of the secondary rectifying tower.
Preferably, the method for introducing the ionic liquid and heavy component mixture into the alkylation reactor comprises:
mixing the ionic liquid and the heavy component mixture with the circulating ionic liquid, and then feeding the mixture into a reactor; or the like, or, alternatively,
mixing the ionic liquid and heavy component mixture with the alkylation raw material and then feeding the mixture into a reactor; or the like, or, alternatively,
the ionic liquid and heavy component mixture directly enters the reactor.
The alkylation equipment comprises an alkylation reactor, a flash tank, a sedimentation separator, a rectifying tower, a hydrogenation reactor and a dechlorination reactor which are sequentially connected through pipelines, wherein the alkylation reactor is provided with a raw material input pipe orifice and a circulating material input pipe orifice, and the top of the alkylation reactor is provided with an alkylation crude product output pipe orifice connected to the flash tank; the top of the flash tank is provided with a first liquefied gas outlet, and the bottom of the flash tank is provided with a liquid-phase component output pipe orifice connected to the sedimentation separator; the top of the settling separator is provided with an output pipe orifice which outputs alkylate oil containing ionic liquid and is connected to the rectifying tower, and the bottom of the settling separator is provided with a first circulating material output pipe orifice which is connected to a circulating pipeline for conveying circulating materials; the top of the rectifying tower is provided with a second liquefied gas outlet, the bottom of the rectifying tower is provided with a second circulating material output pipe orifice connected to the circulating pipeline, and the side of the rectifying tower is provided with a first gasoline conveying pipeline connected to the hydrogenation reactor and used for conveying gasoline components; and a second gasoline conveying pipeline connected to the dechlorination reactor and used for conveying hydrogenated gasoline components is arranged at the top of the hydrogenation reactor.
Preferably, the rectifying tower is a multi-stage rectifying tower.
The method utilizes the characteristic of higher boiling point of the ionic liquid, adopts the existing fractionating tower in the alkylation process, does not additionally increase equipment, thoroughly separates the gasoline in the alkylation product from the heavy component/ionic liquid mixture, returns the heavy component/ionic liquid mixture to an alkylation reactor for continuous reaction, and cracks the heavy component into the gasoline component under the catalysis of the ionic liquid; the gasoline component from the fractionating tower enters a hydrodechlorination reactor, the hydrogenation condition is mild, and the organic matter utilization rate is high. The invention does not adopt alkali washing and water washing processes, does not generate waste alkali and waste water, has small loss of ionic liquid, does not produce heavy components in products and has high utilization rate of hydrocarbons.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
This document provides an overview of various implementations or examples of the technology described in this disclosure, and is not a comprehensive disclosure of the full scope or all features of the disclosed technology.
Drawings
FIG. 1 is a schematic view of the structure of an alkylation apparatus of the present invention
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more clear, the technical solutions of the embodiments of the present disclosure will be described below clearly and completely with reference to the accompanying drawings of the embodiments of the present disclosure. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
To maintain the following description of the embodiments of the present disclosure clear and concise, a detailed description of known functions and known components have been omitted from the present disclosure.
In order to solve the problems that a large amount of ionic liquid is lost and a large amount of waste alkali and waste water are generated due to a large amount of alkali washing and water washing processes used in the alkylation process of the existing ionic liquid catalyst and simultaneously solve the problem that gasoline components contain organic chlorine, the embodiment of the invention provides an alkylation method, wherein C4 alkane and C4 alkene are used as raw materials, and the ionic liquid is used as a catalyst to carry out alkylation reaction in an alkylation reactor; and after the reaction, the components are settled and separated to obtain an alkylated crude product, the alkylated crude product enters a rectifying tower, wherein the liquefied gas component is discharged from the top of the rectifying tower, the mixture of the ionic liquid and the heavy component is discharged from the bottom of the rectifying tower and is conveyed to an alkylation reactor again, the gasoline component is conveyed to a hydrodechlorination reactor through a pipeline arranged at the side of the rectifying tower to be hydrogenated and then enters a dechlorination reactor, and the gasoline component is discharged after dechlorination by a dechlorinating agent in the dechlorination reactor.
In the alkylation process provided by the invention, in some embodiments, the raw material is C4 alkane and C4 alkene, the C4 alkane is preferably isobutane, and the C4 alkene is preferably one or more of 1-butene, 2-butene or isobutene, and preferably 2-butene. It is well known that water causes hydrolysis of ionic liquids and therefore, strict control of the water content or oxygen-containing compounds of the feedstock is required to be less than 10ppm, preferably less than 1 ppm.
The ionic liquid adopted by the catalyst for the alkylation reaction provided by the embodiment of the invention can be various ionic liquids which are publicly reported or recognized to realize catalytic alkylation reaction, and preferably, the anion of the ionic liquid is one or more metal chlorides including aluminum, copper, zinc, tin, titanium and the like; the cation is preferably one of hydrochloride of amine containing alkyl, hydrochloride of imidazole or hydrochloride of pyridine. The manufacturing method can be implemented according to the prior public effective technology.
In addition, in the alkylation method provided in this embodiment, the alkylation reaction conditions may also adopt publicly reported or existing processes, preferably, when the C4 alkane is isobutane, the isobutane is preferably in excess during the reaction, and specifically, the alkane-alkene molar ratio is generally 5: 1-40: 1, the reaction temperature is preferably 0-50 ℃, and the reaction pressure is ensured to keep the raw materials in a liquid phase under the reaction conditions, and is preferably 0.1-1.0 Mpa.
In some embodiments, the alkylation reactor is one of a tank reactor or a tower reactor, and can realize continuous reaction, the alkylation raw material is uniformly mixed and then enters the alkylation reactor from the lower part, the circulating ionic liquid also enters the alkylation reactor from the lower part, after the reaction under the above conditions, the reaction product and the ionic liquid are discharged from the top of the reactor and enter a flash tank, after a large amount of C4 alkane is flashed, the liquid phase enters a settling separator, the preliminary separation is carried out by utilizing the density difference of the alkylate oil and the ionic liquid, the ionic liquid is discharged from the lower part of the settling separator and enters the alkylation reactor for recycling, and the alkylation crude product enters a rectifying tower.
Fig. 1 shows an alkylation apparatus to which the alkylation method of the present invention is applicable, as shown in fig. 1, comprising an alkylation reactor 10, a flash tank 20, a settling separator 30, a rectification column 40, a hydrogenation reactor 50 and a dechlorination reactor 60, which are connected in sequence by pipelines, wherein the alkylation reactor 10 is provided with a raw material input pipe orifice 11 and a circulating material input pipe orifice 13, and the top of the alkylation reactor is provided with an alkylation crude product output pipe orifice 12 connected to the flash tank; the flash tank 20 is provided at the top with a first liquefied gas outlet 21 and at the bottom with a liquid phase component outlet orifice 22 connected to the settling separator 30; the top of the settling separator 30 is provided with an output pipe port 32 which outputs alkylate oil containing ionic liquid and is connected to the rectifying tower 40, and the bottom of the settling separator is provided with a first circulating material output pipe port 31 which is connected to a circulating pipeline 13 for conveying circulating materials; a second liquefied gas outlet 41 is arranged at the top of the rectifying tower 40, a second circulating material output pipe orifice (not labeled in the figure) connected to the circulating pipeline is arranged at the bottom of the rectifying tower, and a first gasoline conveying pipeline 42 connected to the hydrogenation reactor 50 and used for conveying gasoline components is arranged at the side edge of the rectifying tower; the top of the hydrogenation reactor 50 is provided with a second gasoline conveying pipeline 51 connected to the dechlorination reactor 60 for conveying hydrogenated gasoline components.
In some embodiments, the rectification column 40 is a multi-stage rectification column.
In the alkylation method provided by the embodiment of the invention, the ionic liquid can be preferably aluminum trichloride-based ionic liquid, and as the aluminum trichloride-based ionic liquid has no boiling point, the decomposition temperature is about 400 ℃, and the flow range of gasoline components is 30-220 ℃, the gasoline components in the alkylation product can be completely separated from the ionic liquid by utilizing the rectifying tower. The method can adopt a first-stage distillation tower, liquefied gas is discharged from the tower top, gasoline components without ionic liquid are discharged from the lateral line and enter a hydrodechlorination reactor, and a mixture of the ionic liquid and heavy components is discharged from the tower bottom and is circulated to an alkylation reactor. Experiments prove that under the action of the ionic liquid, the recombinant components can undergo cracking reaction to generate gasoline components. For better separation of each component, preferably, a secondary distillation tower can also be adopted, the alkylated crude product enters a secondary rectification tower, the liquefied gas is extracted from the top of the first stage tower, the mixture at the bottom of the tower enters a secondary rectification tower, the gasoline component is extracted from the top of the second stage tower and enters a hydrodechlorination reactor, and the mixture of the ionic liquid and the heavy component is extracted from the bottom of the tower and recycled to the alkylation reactor.
Specifically, the ionic liquid and heavies mixture is recycled to the alkylation reactor in three ways: mixing the ionic liquid and the heavy component mixture with the circulating ionic liquid, and then feeding the mixture into a reactor; or, the mixture of the ionic liquid and the heavy component is mixed with the alkylation raw material and then enters the reactor; alternatively, the ionic liquid and heavies mixture may be fed directly to the reactor.
Hydrodechlorination is a published and commonly used method for petrochemical dechlorination, and preferably, Ni series or Pt, Pd and other precious metal series are often used as catalysts. The alkylation reaction has a chlorine content of not higher than 1000ppm, preferably not higher than 1000ppm, due to strict control of the water content of the raw material, so that dechlorination can be carried out under mild reaction conditions: the temperature is 100-: 1-300: 1; the organic chlorine can be reduced to below 5 ppm.
The hydrogenated gasoline passes through a dechlorination reactor, zinc oxide or other known dechlorination agents capable of adsorbing hydrogen chloride are preferably adopted as dechlorination agents, the generated hydrogen chloride is adsorbed, and the product can enter a finished product tank.
The following preferred examples are provided to illustrate the technical solution of the present invention:
example 1
Feeding cation from Et3NHCl and the anion is provided by AlCl3The provided acidic ionic liquid is used as a catalyst to catalyze alkylation reaction on a continuous device, and the mass ratio of the hourly circulation volume of the ionic liquid to the hourly added total amount of raw materials is 1: 1, the reaction pressure is 0.5MPa, the reaction temperature is 10 ℃, the raw material is a mixture of isobutane and 2-butene, the mole ratio of alkane to alkene is 10: 1, and the water content of the raw material is lower than 10 ppm; the alkylation product enters a flash evaporation tank to flash off a part of liquefied gas, then enters a settling tank to primarily separate ionic liquid, the crude product of the alkylate oil enters a primary rectifying tower, the overhead liquid is used for producing liquefied gas, a mixture of the ionic liquid and heavy components at the bottom of the tower is mixed with the ionic liquid and then enters an alkylation reactor, and the gasoline component discharged from the side line enters a hydrodechlorination reactor; the hydrodechlorination catalyst is a Raney nickel catalyst under the conditions of 120 ℃ of temperature, 1.0MPa of pressure and 2.0h of airspeed-1The volume ratio of hydrogen to oil is 200: 1; and (4) passing the hydrogenation product through a dechlorination tank to obtain a finished product. The conversion rate is determined by analyzing C4 olefin in the liquefied gas by chromatography, Al ions are analyzed by an ICP (inductively coupled plasma) analyzer to monitor the ionic liquid content in the gasoline component, and chlorine element in the gasoline component is monitored by a micro coulometer. The analytical results are shown in Table 1.
Example 2
Feeding cation from Et3NHCl and the anion is provided by AlCl3The provided acidic ionic liquid is used as a catalyst to catalyze alkylation reaction on a continuous device, and the circulation amount of the ionic liquid per hour and the raw materials are added per hourThe total mass ratio is 1: 1, the reaction pressure is 0.5MPa, the reaction temperature is 10 ℃, the raw material is a mixture of isobutane and 2-butene, the mole ratio of alkane to alkene is 10: 1, and the water content of the raw material is lower than 10 ppm; the alkylation product enters a flash evaporation tank to be flashed with a part of liquefied gas, then enters a settling tank to be primarily separated into ionic liquid, the crude product of the alkylate oil enters a primary rectifying tower, the overhead liquid is used for discharging the liquefied gas, the mixture of the ionic liquid and the heavy component at the bottom of the tower is mixed with the alkylation raw material and then enters an alkylation reactor, and the gasoline component discharged from the side line enters a hydrodechlorination reactor; the hydrodechlorination catalyst is a Raney nickel catalyst under the conditions of 120 ℃ of temperature, 1.0MPa of pressure and 2.0h of airspeed-1The volume ratio of hydrogen to oil is 200: 1; and (4) passing the hydrogenation product through a dechlorination tank to obtain a finished product. The conversion rate is determined by analyzing C4 olefin in the liquefied gas by chromatography, Al ions are analyzed by an ICP (inductively coupled plasma) analyzer to monitor the ionic liquid content in the gasoline component, and chlorine element in the gasoline component is monitored by a micro coulometer. The analytical results are shown in Table 1.
Example 3
Feeding cation from Et3NHCl and the anion is provided by AlCl3The provided acidic ionic liquid is used as a catalyst to catalyze alkylation reaction on a continuous device, and the mass ratio of the hourly circulation volume of the ionic liquid to the hourly added total amount of raw materials is 1: 1, the reaction pressure is 0.5MPa, the reaction temperature is 10 ℃, the raw material is a mixture of isobutane and 2-butene, the mole ratio of alkane to alkene is 10: 1, and the water content of the raw material is lower than 10 ppm; the alkylate product enters a flash evaporation tank to flash off a part of liquefied gas, then enters a settling tank to primarily separate ionic liquid, the crude alkylate oil enters a primary rectifying tower, the overhead liquid is liquefied, the mixture of the ionic liquid and the heavy component at the bottom of the tower directly enters an alkylation reactor, and the gasoline component discharged from the side line enters a hydrodechlorination reactor; the hydrodechlorination catalyst is a Raney nickel catalyst under the conditions of 120 ℃ of temperature, 1.0MPa of pressure and 2.0h of airspeed-1The volume ratio of hydrogen to oil is 200: 1; and (4) passing the hydrogenation product through a dechlorination tank to obtain a finished product. The conversion rate is determined by analyzing C4 olefin in the liquefied gas by chromatography, Al ions are analyzed by an ICP (inductively coupled plasma) analyzer to monitor the ionic liquid content in the gasoline component, and chlorine element in the gasoline component is monitored by a micro coulometer. The analytical results are shown in Table 1.
Example 4
Feeding cation from Et3NHCl and the anion is provided by AlCl3The provided acidic ionic liquid is used as a catalyst to catalyze isobutane alkylation reaction on a continuous device, and the mass ratio of the hourly circulation amount of the ionic liquid to the hourly added total amount of raw materials is 1: 1, the reaction pressure is 0.5MPa, the reaction temperature is 10 ℃, the raw material is a mixture of isobutane and 2-butene, the mole ratio of alkane to alkene is 10: 1, and the water content of the raw material is lower than 10 ppm; the alkylation product enters a flash tank to flash off a part of liquefied gas, then enters a settling tank to primarily separate ionic liquid, the crude product of the alkylate oil enters a secondary rectifying tower, the liquefied gas is discharged from the top of the primary tower, the mixture at the bottom of the primary tower enters a secondary rectifying tower, the mixture of the ionic liquid and the heavy component at the bottom of the secondary tower is mixed with the alkylation raw material and then enters an alkylation reactor, and the gasoline component discharged from the top of the secondary tower enters a hydrodechlorination reactor; the hydrodechlorination catalyst is a Raney nickel catalyst under the conditions of 120 ℃ of temperature, 1.0MPa of pressure and 2.0h of airspeed-1The volume ratio of hydrogen to oil is 200: 1; and (4) passing the hydrogenation product through a dechlorination tank to obtain a finished product. The conversion rate is determined by analyzing C4 olefin in the liquefied gas by chromatography, Al ions are analyzed by an ICP (inductively coupled plasma) analyzer to monitor the ionic liquid content in the gasoline component, and chlorine element in the gasoline component is monitored by a micro coulometer. The analytical results are shown in Table 1.
Example 5
Feeding cation from Et3NHCl and the anion is provided by AlCl3The provided acidic ionic liquid is used as a catalyst to catalyze isobutane alkylation reaction on a continuous device, and the mass ratio of the hourly circulation amount of the ionic liquid to the hourly added total amount of raw materials is 1: 1, the reaction pressure is 0.5MPa, the reaction temperature is 10 ℃, the raw material is a mixture of isobutane and 2-butene, the mole ratio of alkane to alkene is 10: 1, and the water content of the raw material is lower than 10 ppm; the alkylation product enters a flash tank to flash off a part of liquefied gas, then enters a settling tank to primarily separate ionic liquid, the crude product of the alkylate oil enters a secondary rectifying tower, the liquefied gas is discharged from the top of the primary tower, the mixture at the bottom of the primary tower enters a secondary rectifying tower, the mixture of the ionic liquid and the heavy component at the bottom of the secondary tower is mixed with the ionic liquid and then enters an alkylation reactor, and the gasoline component discharged from the top of the secondary tower enters a hydrodechlorination reactor; hydrodechlorinationThe catalyst is Raney nickel catalyst, the temperature is 120 ℃, the pressure is 1.0MPa, and the space velocity is 2.0h-1The volume ratio of hydrogen to oil is 200: 1; and (4) passing the hydrogenation product through a dechlorination tank to obtain a finished product. The conversion rate is determined by analyzing C4 olefin in the liquefied gas by chromatography, Al ions are analyzed by an ICP (inductively coupled plasma) analyzer to monitor the ionic liquid content in the gasoline component, and chlorine element in the gasoline component is monitored by a micro coulometer. The analytical results are shown in Table 1.
Comparative example 1
Feeding cation from Et3NHCl and the anion is provided by AlCl3The provided acidic ionic liquid is used as a catalyst to catalyze isobutane alkylation reaction on a continuous device, and the mass ratio of the hourly circulation amount of the ionic liquid to the hourly added total amount of raw materials is 1: 1, the reaction pressure is 0.5MPa, the reaction temperature is 10 ℃, the raw material is a mixture of isobutane and 2-butene, the mole ratio of alkane to alkene is 10: 1, and the water content of the raw material is lower than 10 ppm; the alkylate product enters a flash evaporation tank to flash off a part of liquefied gas, then enters a settling tank to primarily separate ionic liquid, the alkylate crude product enters a secondary settling tank to separate the ionic liquid again, and then enters hydrodechlorination through primary alkali washing and tertiary water washing; the hydrodechlorination catalyst is a Raney nickel catalyst under the conditions of 120 ℃ of temperature, 1.0MPa of pressure and 2.0h of airspeed-1The volume ratio of hydrogen to oil is 200: 1; and (4) passing the hydrogenation product through a dechlorination tank to obtain a finished product. And (3) determining the conversion rate by analyzing C4 olefin in the liquefied gas by chromatography, monitoring the ionic liquid content in the gasoline component alkylate oil after secondary sedimentation by analyzing Al ions by an ICP (inductively coupled plasma) analyzer, and monitoring the chlorine element in the gasoline component alkylate oil by a micro coulometer. The analytical results are shown in Table 1.
TABLE 1
Figure BDA0002517589340000091
Compared with the prior art, the alkylation method provided by the embodiment of the invention has the following beneficial effects:
1. the alkylation method of the invention has no alkali washing and water washing processes, no waste alkali and waste water, is environment-friendly, has small loss amount of ionic liquid and reduces the cost.
2. The invention increases the gasoline yield through the heavy component cycle cracking reaction, and provides economic benefit.
3. The invention recovers the organic part of the chlorohydrocarbon through the hydrodechlorination reaction, increases the yield of the gasoline and provides economic benefits.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should also be considered as falling within the scope of the present invention.

Claims (10)

1. An alkylation method, which takes C4 alkane and C4 alkene as raw materials and takes ionic liquid as a catalyst to carry out alkylation reaction in an alkylation reactor; and after the reaction, the components are settled and separated to obtain an alkylated crude product, the alkylated crude product enters a rectifying tower, wherein the liquefied gas component is discharged from the top of the rectifying tower, the mixture of the ionic liquid and the heavy component is discharged from the bottom of the rectifying tower and is conveyed to an alkylation reactor again, the gasoline component is conveyed to a hydrodechlorination reactor through a pipeline arranged at the side of the rectifying tower to be hydrogenated and then enters a dechlorination reactor, and the gasoline component is discharged after dechlorination by a dechlorinating agent in the dechlorination reactor.
2. The alkylation process of claim 1, wherein the C4 olefin is selected from 1-butene, 2-butene or isobutene, or a mixture thereof; the C4 alkane is isobutane.
3. The alkylation process of claim 1, the C4 alkane and the C4 alkene having a water or oxygenate content of less than 10 ppm.
4. The alkylation process of claim 1, wherein the ionic liquid has one or more metal chlorides as an anion; the cation of the ionic liquid is one or more of hydrochloride of amine containing alkyl, hydrochloride of imidazole or hydrochloride of pyridine.
5. The alkylation process of claim 1, wherein the alkylation reaction conditions are: the molar ratio of the C4 alkane to the C4 alkene is 5: 1-40: 1, the reaction temperature is 0-50 ℃, and the reaction pressure is 0.1-1.0 Mpa.
6. The alkylation process of claim 1, wherein the reacted components after the alkylation reaction include reaction product and ionic liquid, and wherein the reacted components exit the top of the alkylation reactor and enter a flash tank, and wherein the liquid phase enters a settling separator for settling separation after flashing off the C4 alkane.
7. The alkylation method of claim 1, wherein after the crude product of the alkylation enters a primary rectifying tower, liquefied gas is discharged from the top of the primary rectifying tower, gasoline components are discharged from the side edge of the primary rectifying tower, and a mixture of ionic liquid and heavy components is extracted from the bottom of the primary rectifying tower; or the alkylated crude product enters a secondary rectifying tower, liquefied gas is discharged from the top of the primary rectifying tower, and the mixture at the bottom of the tower enters the secondary rectifying tower; and discharging gasoline components from the top of the secondary rectifying tower, and extracting a mixture of ionic liquid and heavy components from the bottom of the secondary rectifying tower.
8. The alkylation process of claim 1, wherein the ionic liquid and heavies mixture is introduced into the alkylation reactor by a process comprising:
mixing the ionic liquid and the heavy component mixture with the circulating ionic liquid, and then feeding the mixture into a reactor; or the like, or, alternatively,
mixing the ionic liquid and heavy component mixture with the alkylation raw material and then feeding the mixture into a reactor; or the like, or, alternatively,
the ionic liquid and heavy component mixture directly enters the reactor.
9. An alkylation device comprises an alkylation reactor, a flash tank, a settling separator, a rectifying tower, a hydrogenation reactor and a dechlorination reactor which are sequentially connected through pipelines, wherein a raw material input pipe orifice and a circulating material input pipe orifice are arranged on the alkylation reactor, and an alkylation crude product output pipe orifice connected to the flash tank is arranged at the top of the alkylation reactor; the top of the flash tank is provided with a first liquefied gas outlet, and the bottom of the flash tank is provided with a liquid-phase component output pipe orifice connected to the sedimentation separator; the top of the settling separator is provided with an output pipe orifice which outputs alkylate oil containing ionic liquid and is connected to the rectifying tower, and the bottom of the settling separator is provided with a first circulating material output pipe orifice which is connected to a circulating pipeline for conveying circulating materials; the top of the rectifying tower is provided with a second liquefied gas outlet, the bottom of the rectifying tower is provided with a second circulating material output pipe orifice connected to the circulating pipeline, and the side of the rectifying tower is provided with a first gasoline conveying pipeline connected to the hydrogenation reactor and used for conveying gasoline components; and a second gasoline conveying pipeline connected to the dechlorination reactor and used for conveying hydrogenated gasoline components is arranged at the top of the hydrogenation reactor.
10. The alkylation apparatus of claim 9, wherein the rectification column is a multi-stage rectification column.
CN202010481561.3A 2020-05-31 2020-05-31 Alkylation method and alkylation equipment Pending CN111592912A (en)

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US20040133056A1 (en) * 2002-11-12 2004-07-08 Zhichang Liu Method for manufacturing alkylate oil with composite ionic liquid used as catalyst
US20100193401A1 (en) * 2007-07-13 2010-08-05 Instituto Mexicano Del Petroleo Ionic Liquid Catalyst for Improvement of Heavy and Extra Heavy Crude
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