CN107739300B - Process method for producing high-purity isobutene and ethylene glycol mono-tert-butyl ether - Google Patents
Process method for producing high-purity isobutene and ethylene glycol mono-tert-butyl ether Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- C07C7/005—Processes comprising at least two steps in series
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- C07C7/04—Purification; Separation; Use of additives by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P30/40—Ethylene production
Abstract
The invention discloses a production process for simultaneously producing high-purity isobutene and ethylene glycol tert-butyl ether, belonging to the field of chemical product process production. The production process comprises the steps of generating a crude product of ethylene glycol mono-tert-butyl ether by ethylene glycol and isobutene in mixed C4 under the action of a solid catalyst, and preparing an ethylene glycol mono-tert-butyl ether product by rectifying and purifying part of the crude product of the ethylene glycol mono-tert-butyl ether; the rest part of crude ethylene glycol mono-tert-butyl ether is subjected to cracking reaction under the action of a solid catalyst to generate a high-purity isobutene product. Compared with the traditional process for preparing high-purity isobutene, the process has the advantages of simple process flow, small equipment investment, easy product separation, low energy consumption, good product quality and the like; meanwhile, the novel environment-friendly solvent ethylene glycol mono-tert-butyl ether can be produced, the market risk resistance of the device is improved, and the total production cost is reduced; is an advanced process method.
Description
Technical Field
The invention relates to the technical field of chemical product production processes, in particular to a process method for producing high-purity isobutene and ethylene glycol tert-butyl ether
Background
High purity isobutylene generally refers to products having an isobutylene purity greater than 99.5% to distinguish it from isobutylene which is a mixed fraction from petroleum refineries and ethylene steam cracking units. The high-purity isobutene can be applied to fine chemicals such as butyl rubber, polyisobutylene, methacrylate (MMA), tert-butyl mercaptan, tert-butyl phenol, an antioxidant, tert-butylamine and other various organic chemical products, and the total demand of the high-purity isobutene in the world in 2018 is estimated to reach 260 million tons, so that the market demand is huge.
The major suppliers of high purity isobutene in the world today are Lyondell Basell, Exxon Mobil, Texas Petrochemicals (TPC), Russian Nizhnekamskneftehim (NKNK), Evonik, Japanese Sumitomo, and the like. The devices except Lyondell Basell in three production places all over the world and Korean pine original company device adopt tert-butyl alcohol hydrolysis process to prepare high-purity isobutene, and other devices mostly adopt MTBE cracking process to prepare high-purity isobutene. Although the MTBE cracking process is mature, the process is complex, the flow is long, the gas phase cracking is carried out, the temperature is high, dimethyl ether is easily generated in the cracking process, and the separation and purification difficulty is high; the equipment is more, the investment is large, the energy consumption is high, and the production cost is high. Although the tertiary butanol hydrolysis process has simple process flow, low equipment investment and mild process conditions; but the tertiary butanol dehydration single pass conversion rate is low, the total energy consumption is large, and the production cost is also higher.
The technology for preparing high-purity isobutene by ethylene glycol tert-butyl Ether (ETB) cracking disclosed by the patent has the advantages of simple process flow, small equipment investment, easy product separation and the like, and also has the advantages of high single-pass conversion rate, low energy consumption, good isobutene product quality, low production cost and the like; is an ideal new process for preparing high-purity isobutene.
Meanwhile, ethylene glycol mono-tert-butyl Ether (ETB) is used as a product with low photochemical reactivity, can be used as a substituted solvent for replacing ethylene glycol butyl Ether (EB) in some fields, and is a novel environment-friendly solvent. Compared with EB, ETB has the advantages of good water solubility, good latex dispersion stability, good aqueous solution volatility, mild skin irritation, low photochemical reaction and the like; can be widely applied to the fields of coatings, printing ink, household cleaning agents and the like. Therefore, the process can produce the ETB product for export sales according to market conditions while producing the high-purity isobutene product, and the device income and the market risk resistance are increased.
Disclosure of Invention
Aiming at the problems of complex production process, high energy consumption, difficult product separation, high production cost and the like of high-purity isobutene in China, the invention adopts high-boiling point dihydric alcohol glycol to replace methanol and develops a process method capable of simultaneously producing high-purity isobutene and a novel environment-friendly solvent, namely ethylene glycol mono-tert-butyl ether. The process method has the advantages of simple process flow, energy conservation, environmental protection, good product quality, small equipment investment, low production cost and the like, and has high application value and economic benefit.
The specific technical scheme of the invention is as follows:
a process for producing isobutene and ethylene glycol mono-tert-butyl ether comprises the following steps: an etherification reaction unit, an ethylene glycol mono-tert-butyl ether product unit and a high-purity isobutene product unit.
The production process of the etherification reaction unit comprises the following steps:
(1) feeding the mixed carbon four containing isobutene into a carbon four buffer tank, boosting the pressure by a mixed carbon four feeding pump, and then feeding the mixture into a static mixer to be fully mixed with ethylene glycol;
(2) feeding fresh ethylene glycol and recycled ethylene glycol into an ethylene glycol buffer tank, boosting the pressure by an ethylene glycol feed pump, feeding the ethylene glycol into an ethylene glycol purifier, feeding one part of the ethylene glycol without trace impurities into a static mixer to be fully mixed with mixed C4, and feeding the other part of the ethylene glycol into the top of a catalytic rectifying tower to continuously react with unreacted isobutene in an etherification reactor;
(3) heating the fully mixed ethylene glycol and mixed C4 by a preheater to a certain temperature, then feeding the heated mixture into a fixed bed etherification reactor, and reacting most of isobutene in the mixed C4 with the ethylene glycol to generate ethylene glycol mono-tert-butyl ether or ethylene glycol di-tert-butyl ether under the action of an etherification catalyst;
(4) the reaction product of the etherification reactor enters a catalytic rectification tower, light component mixed carbon four enters a reaction section filled with the etherification catalyst at the upper part of the tower after rectification, unreacted isobutene in the mixed carbon four continuously reacts with ethylene glycol under the action of the etherification catalyst, the remaining carbon four is evaporated from the top of the tower, the condensed liquid enters a reflux tank of the catalytic rectification tower after being condensed by a circulating condenser, part of the condensed liquid is taken as reflux liquid by a reflux pump of the catalytic rectification tower and is sent to the top of the tower, and part of the carbon four is sold as an etherified carbon four product; and (3) after the heavy component ethylene glycol mono-tert-butyl ether crude product is subjected to heat exchange and temperature reduction by a heat exchanger, feeding the heavy component ethylene glycol mono-tert-butyl ether crude product into a buffer tank of the ethylene glycol mono-tert-butyl ether crude product.
The step (1) is characterized in that: the content of isobutene in the mixed C4 is 1-90%.
The step (2) is characterized in that:
the ethylene glycol purifier is filled with a molecular sieve catalyst, which is mainly used for removing trace water in the ethylene glycol and reducing the generation amount of the byproduct tertiary butanol.
The step (3): the feeding proportion of the ethylene glycol and the mixed C4 is that the molar ratio of the ethylene glycol to the isobutene in the mixed C4 is 1: 0.5-2; the preheating temperature of the preheater is 30-80 ℃; the etherification reaction temperature is 40-100 ℃; the feeding mass space velocity of the ethylene glycol is 0.5-3.0h-1(ii) a The etherification pressure is 0.5-5.0 Mpa; the conversion rate of isobutene is 80-95%; the etherification catalyst is one of modified strong acid cation resin catalyst, solid heteropoly acid catalyst, modified molecular sieve catalyst and solid super strong acid catalyst.
The step (4): the pressure of the catalytic rectifying tower is 0.5-1.5Mpa, the reaction temperature of the reaction section of the catalytic rectifying tower is 40-100 ℃, and the molar ratio of the ethylene glycol to the isobutene of the reaction section of the catalytic rectifying tower is 1: 0.5-2.0.
The unit production process of the ethylene glycol mono-tert-butyl ether product comprises the following steps:
(1) feeding a part of ethylene glycol mono-tert-butyl ether crude product in an ethylene glycol mono-tert-butyl ether crude product buffer tank into a light component removing tower for rectification, and distilling out light components of isobutene dimer and tert-butyl alcohol from the top of the tower; heavy components at the bottom of the tower enter a diether removing tower;
(2) the heavy components at the bottom of the ethylene glycol mono-tert-butyl ether lightness-removing tower enter a double ether removing tower and then form a water-ethylene glycol mono-tert-butyl ether-ethylene glycol double-tert-butyl ether azeotropic system with water entering the tower, and the water-ethylene glycol mono-tert-butyl ether-ethylene glycol double-tert-butyl ether azeotrope is distilled at the top of the tower and then enters a phase separation tank after being condensed; the heavy components at the bottom of the tower enter a glycol mono-tert-butyl ether separation tower;
(3) the oil phase in the phase separation tank enters an oil phase receiving tank through overflow, and the oil phase in the oil phase receiving tank is sent to a cracking reactor through a discharge pump of the oil phase tank for reaction; the water phase enters a water phase receiving tank from the bottom of the phase separation tank, one part of water in the water phase receiving tank enters a diether rectifying tower from the tower through a water phase reflux pump, and the other part of water flows back to the tower from the top of the tower, so that the water is recycled;
(4) heavy components at the bottom of the double ether removal tower enter a single ether removal tower to be continuously rectified, ethylene glycol mono-tert-butyl ether is extracted from a side line of the tower and sent to an ethylene glycol mono-tert-butyl product storage tank to be sold as a product; condensing the light components evaporated from the tower top, feeding a part of the condensed light components into the tower for refluxing, and feeding a part of the condensed light components into a phase splitting tank; and (3) sending the heavy component ethylene glycol at the bottom of the tower into a recovered ethylene glycol storage tank for recycling.
The step (1): the temperature of the top of the rectifying tower of the ethylene glycol mono-tert-butyl ether lightness-removing tower is 40-80 ℃, and the rectifying pressure is 10-200 kpa.
The step (2): the mass ratio of the entrainer water to the ethylene glycol di-tert-butyl ether is as follows: 1: 0.1-5.0; the temperature at the top of the tower is 40-80 ℃, and the rectification pressure is 10-100 kpa.
The step (4): the temperature of the top of the monoether removing tower is 80-150 ℃, and the rectification pressure is 10-100 kpa; the content of ethylene glycol mono-tert-butyl ether product is more than 99%, and the content of ethylene glycol is more than 99%.
The unit production process of the high-purity isobutene product comprises the following steps:
(1) mixing the ethylene glycol mono-tert-butyl ether crude product with the oil phase in the oil phase receiving tank, then feeding the mixture into a cracking reactor preheater, heating the mixture to a certain temperature, and feeding the mixture into a cracking reactor; under the catalytic action of a cracking catalyst, ethylene glycol mono-tert-butyl ether and ethylene glycol di-tert-butyl ether are subjected to cracking reaction to generate a mixture of ethylene glycol and isobutene;
(2) the products of the cracking reactor enter an ethylene glycol flash tower, and light components and heavy components are primarily separated;
(3, distilling light components in the ethylene glycol flash tower from the top, then rectifying and purifying the light components in an isobutene de-weighting tower, distilling a high-purity isobutene product from the top, condensing the high-purity isobutene product, and then sending the condensed high-purity isobutene product to a high-purity isobutene product storage tank;
(4) the heavy component of the ethylene glycol flash tower enters an ethylene glycol light component removal tower to be continuously rectified, the light component is evaporated from the top of the ethylene glycol light component removal tower, and the condensed light component is sent to a byproduct storage tank; feeding heavy components at the bottom of the tower into an ethylene glycol de-heavy tower;
(5) the heavy component of the ethylene glycol light component removal tower enters an ethylene glycol heavy component removal tower to be continuously rectified, a part of the light component evaporated from the tower top is sent into the tower to reflux after being condensed, the other part of the light component is sent into an ethylene glycol recovery tank to be recycled, and the heavy component at the tower bottom is sent into a diethylene glycol product storage tank after being condensed.
The preheating temperature of the cracking reactor in the step (1) is 60-200 ℃, the cracking reaction temperature is 70-150 ℃, and the feeding mass space velocity of the cracking raw material is 0.5-3.0h-1The cracking reaction pressure is 0-0.5MPa, and the cracking reaction catalyst is one of modified strong acid cation resin catalyst, solid heteropoly acid catalyst, modified molecular sieve catalyst and solid super strong acid catalyst.
The step (1): the cracking reactor is of a tubular reactor type.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Example 1
Mixing four carbon materials with 30 percent of isobutene content and 99 percent of glycol materials purified by a purifier according to the proportion of glycol and isobuteneFully mixing the components in a molar ratio of 1.5:1, and preheating the mixture to 75 ℃ through a preheater; the reaction pressure is 1.5MPa, the reaction temperature is 80 ℃, and the mass space velocity of the ethylene glycol is 2.0h-1Under the reaction condition of (3), the preheated raw material passes through a fixed bed reactor loaded with an etherification catalyst to catalyze isobutene in the mixed C4 to react with ethylene glycol to generate ethylene glycol mono-tert-butyl ether or ethylene glycol di-tert-butyl ether. The isobutene content in the mixed C4 after the reaction in the reaction section is less than 4 percent, and the isobutene conversion rate is more than 90 percent.
Feeding the reaction product into a catalytic rectification tower, feeding the rectified light component mixed C4 into a reaction section filled with an etherification catalyst at the upper part of the tower, continuously reacting unreacted isobutene in the mixed C4 with ethylene glycol under the action of the etherification catalyst, keeping the pressure of the catalytic rectification tower at 1.0MPa, keeping the temperature of the reaction section at the top of the tower at 80 ℃, and ensuring that the molar ratio of the ethylene glycol to the unreacted isobutene is 1.5:1, so that the isobutene in the mixed C4 is fully reacted, the isobutene content in the remaining mixed C4 is less than 0.4 percent, and the isobutene conversion rate is more than 99 percent. And evaporating the residual C4 from the tower top, condensing to obtain the C4 product which is taken out after being etherified. And (3) after the heavy component ethylene glycol mono-tert-butyl ether crude product is subjected to heat exchange and temperature reduction by a heat exchanger, feeding the heavy component ethylene glycol mono-tert-butyl ether crude product into a buffer tank of the ethylene glycol mono-tert-butyl ether crude product to obtain the ethylene glycol mono-tert-butyl ether crude product.
Feeding a part of crude ethylene glycol mono-tert-butyl ether into an ethylene glycol mono-tert-butyl ether lightness-removing tower, and collecting light-component isobutene dimer, tert-butyl alcohol and other by-products under the conditions of rectification pressure of 100KPa and tower top temperature of 70 ℃. And then sending the heavy component at the bottom of the tower into a double ether removing tower, simultaneously adding water with the mass ratio of 1:1 to the ethylene glycol di-tert-butyl ether in the heavy component as an entrainer, and extracting the azeotrope of the ethylene glycol di-tert-butyl ether, the water and the ethylene glycol mono-tert-butyl ether under the conditions that the rectification pressure is 50KPa and the tower top temperature is 50 ℃. And then, sending heavy components at the bottom of the tower into a monoether removing tower, and extracting an ethylene glycol mono-tert-butyl ether product with the content of more than 99% from the side line of the tower under the conditions that the rectification pressure is 20KPa and the temperature at the top of the tower is 100 ℃. The product index parameters are shown in the following table:
preheating a part of crude ethylene glycol mono-tert-butyl ether to 150 ℃ by a preheater, and then cracking raw material feeding mass space velocity is 2.0h at the reaction pressure of 0.1MPa and the reaction temperature of 150 DEG C-1Carrying out cracking reaction through a tubular reactor filled with a cracking catalyst under the condition to generate a mixture of isobutene and ethylene glycol; isobutene in the mixture is separated by an ethylene glycol flash tower, and is purified by an isobutene de-heavy tower to obtain a high-purity isobutene product, wherein the indexes of the high-purity isobutene product are shown in the following table:
| serial number | Name (R) | Detecting the index |
| 1 | Isobutene | 99.95％ |
| 2 | Isobutane | 150ppm |
| 3 | Butene-1 | 8ppm |
| 4 | Cis-buten-2 | 20ppm |
| 5 | Tert-butyl alcohol | 5ppm |
| 6 | Water (W) | 5ppm |
| 7 | Ethylene glycol | 1ppm |
| 8 | Sulfur | 1mg/m3 |
| 9 | Dimer | 5ppm |
Example 2
Fully mixing a mixed C-C raw material with the isobutene content of 50% and a glycol raw material with the content of 99% purified by a purifier according to the molar ratio of 1.5:1 of glycol to isobutene, and preheating to 75 ℃ by a preheater; the reaction pressure is 1.5MPa, the reaction temperature is 80 ℃, and the mass space velocity of the ethylene glycol is 2.0h-1Under the reaction condition of (3), the preheated raw material passes through a fixed bed reactor loaded with an etherification catalyst to catalyze isobutene in the mixed C4 to react with ethylene glycol to generate ethylene glycol mono-tert-butyl ether or ethylene glycol di-tert-butyl ether. The isobutene content in the mixed C4 after the reaction in the reaction section is less than 6 percent, and the isobutene conversion rate is more than 90 percent.
Feeding the reaction product into a catalytic rectification tower, feeding the rectified light component mixed C4 into a reaction section filled with an etherification catalyst at the upper part of the tower, continuously reacting unreacted isobutene in the mixed C4 with ethylene glycol under the action of the etherification catalyst, keeping the pressure of the catalytic rectification tower at 1.0MPa, keeping the temperature of the reaction section at the top of the tower at 80 ℃, and ensuring that the molar ratio of the ethylene glycol to the unreacted isobutene is 1.5:1, so that the isobutene in the mixed C4 is fully reacted, the isobutene content in the remaining mixed C4 is less than 0.4 percent, and the isobutene conversion rate is more than 99 percent. And evaporating the residual C4 from the tower top, condensing to obtain the C4 product which is taken out after being etherified. And (3) after the heavy component ethylene glycol mono-tert-butyl ether crude product is subjected to heat exchange and temperature reduction by a heat exchanger, feeding the heavy component ethylene glycol mono-tert-butyl ether crude product into a buffer tank of the ethylene glycol mono-tert-butyl ether crude product to obtain the ethylene glycol mono-tert-butyl ether crude product.
Feeding a part of crude ethylene glycol mono-tert-butyl ether into an ethylene glycol mono-tert-butyl ether lightness-removing tower, and collecting light-component isobutene dimer, tert-butyl alcohol and other by-products under the conditions of rectification pressure of 100KPa and tower top temperature of 70 ℃. And then sending the heavy component at the bottom of the tower into a double ether removing tower, simultaneously adding water with the mass ratio of 1:1 to the ethylene glycol di-tert-butyl ether in the heavy component as an entrainer, and extracting the azeotrope of the ethylene glycol di-tert-butyl ether, the water and the ethylene glycol mono-tert-butyl ether under the conditions that the rectification pressure is 50KPa and the tower top temperature is 50 ℃. And then, sending heavy components at the bottom of the tower into a monoether removing tower, and extracting an ethylene glycol mono-tert-butyl ether product with the content of more than 99% from the side line of the tower under the conditions that the rectification pressure is 20KPa and the temperature at the top of the tower is 100 ℃. The product index parameters are shown in the following table:
preheating a part of crude ethylene glycol mono-tert-butyl ether to 150 ℃ by a preheater, and then cracking raw material feeding mass space velocity is 2.0h at the reaction pressure of 0.1MPa and the reaction temperature of 150 DEG C-1Carrying out cracking reaction through a tubular reactor filled with a cracking catalyst under the condition to generate a mixture of isobutene and ethylene glycol; isobutene in the mixture is separated by an ethylene glycol flash tower, and is purified by an isobutene de-heavy tower to obtain a high-purity isobutene product, wherein the indexes of the high-purity isobutene product are shown in the following table:
| serial number | Name (R) | Detecting the index |
| 1 | Isobutene | 99.92％ |
| 2 | Isobutane | 180ppm |
| 3 | Butene-1 | 8ppm |
| 4 | Cis-buten-2 | 20ppm |
| 5 | Tert-butyl alcohol | 5ppm |
| 6 | Water (W) | 8ppm |
| 7 | Ethylene glycol | 1ppm |
| 8 | Sulfur | 1mg/m3 |
| 9 | Dimer | 6ppm |
Example 3
Fully mixing a mixed C-C raw material with the isobutene content of 70% and a glycol raw material with the content of 99% purified by a purifier according to the molar ratio of 1.5:1 of glycol to isobutene, and preheating to 75 ℃ by a preheater; the reaction pressure is 1.5MPa, the reaction temperature is 80 ℃, and the mass space velocity of the ethylene glycol is 2.0h-1Under the reaction condition of (3), the preheated raw material passes through a fixed bed reactor loaded with an etherification catalyst to catalyze isobutene in the mixed C4 to react with ethylene glycol to generate ethylene glycol mono-tert-butyl ether or ethylene glycol di-tert-butyl ether. The isobutene content in the mixed C4 after the reaction in the reaction section is less than 8 percent, and the isobutene conversion rate is more than 90 percent.
Feeding the reaction product into a catalytic rectification tower, feeding the rectified light component mixed C4 into a reaction section filled with an etherification catalyst at the upper part of the tower, continuously reacting unreacted isobutene in the mixed C4 with ethylene glycol under the action of the etherification catalyst, keeping the pressure of the catalytic rectification tower at 1.0MPa, keeping the temperature of the reaction section at the top of the tower at 80 ℃, and ensuring that the molar ratio of the ethylene glycol to the unreacted isobutene is 1.5:1, so that the isobutene in the mixed C4 is fully reacted, the isobutene content in the remaining mixed C4 is less than 0.4 percent, and the isobutene conversion rate is more than 99 percent. And evaporating the residual C4 from the tower top, condensing to obtain the C4 product which is taken out after being etherified. And (3) after the heavy component ethylene glycol mono-tert-butyl ether crude product is subjected to heat exchange and temperature reduction by a heat exchanger, feeding the heavy component ethylene glycol mono-tert-butyl ether crude product into a buffer tank of the ethylene glycol mono-tert-butyl ether crude product to obtain the ethylene glycol mono-tert-butyl ether crude product.
Feeding a part of crude ethylene glycol mono-tert-butyl ether into an ethylene glycol mono-tert-butyl ether lightness-removing tower, and collecting light-component isobutene dimer, tert-butyl alcohol and other by-products under the conditions of rectification pressure of 100KPa and tower top temperature of 70 ℃. And then sending the heavy component at the bottom of the tower into a double ether removing tower, simultaneously adding water with the mass ratio of 1:1 to the ethylene glycol di-tert-butyl ether in the heavy component as an entrainer, and extracting the azeotrope of the ethylene glycol di-tert-butyl ether, the water and the ethylene glycol mono-tert-butyl ether under the conditions that the rectification pressure is 50KPa and the tower top temperature is 50 ℃. And then, sending heavy components at the bottom of the tower into a monoether removing tower, and extracting an ethylene glycol mono-tert-butyl ether product with the content of more than 99% from the side line of the tower under the conditions that the rectification pressure is 20KPa and the temperature at the top of the tower is 100 ℃. The product index parameters are shown in the following table:
preheating a part of crude ethylene glycol mono-tert-butyl ether to 150 ℃ by a preheater, and then cracking raw material feeding mass space velocity is 2.0h at the reaction pressure of 0.1MPa and the reaction temperature of 150 DEG C-1Carrying out cracking reaction through a tubular reactor filled with a cracking catalyst under the condition to generate a mixture of isobutene and ethylene glycol; isobutene in the mixture is separated by an ethylene glycol flash tower, and is purified by an isobutene de-heavy tower to obtain a high-purity isobutene product, wherein the indexes of the high-purity isobutene product are shown in the following table:
| serial number | Name (R) | Detecting the index |
| 1 | Isobutene | 99.98％ |
| 2 | Isobutane | 120ppm |
| 3 | Butene-1 | 5ppm |
| 4 | Cis-buten-2 | 20ppm |
| 5 | Tert-butyl alcohol | 5ppm |
| 6 | Water (W) | 6ppm |
| 7 | Ethylene glycol | 1ppm |
| 8 | Sulfur | 1mg/m3 |
| 9 | Dimer | 4ppm |
Example 4
Fully mixing a mixed C-C raw material with the content of isobutene of 30% and a glycol raw material with the content of 99% purified by a purifier according to the molar ratio of 2.0:1 of glycol to isobutene, and preheating to 75 ℃ by a preheater; the reaction pressure is 1.5MPa, the reaction temperature is 80 ℃, and the mass space velocity of the ethylene glycol is 2.0h-1Under the reaction condition of (3), the preheated raw material passes through a fixed bed reactor loaded with an etherification catalyst to catalyze isobutene in the mixed C4 to react with ethylene glycol to generate ethylene glycol mono-tert-butyl ether or ethylene glycol di-tert-butyl ether. After the reaction in this stage, the difference in carbon four is mixedThe content of butylene is less than 3 percent, and the conversion rate of isobutylene is more than 92 percent.
Feeding the reaction product into a catalytic rectification tower, feeding the rectified light component mixed C4 into a reaction section filled with an etherification catalyst at the upper part of the tower, continuously reacting unreacted isobutene in the mixed C4 with ethylene glycol under the action of the etherification catalyst, keeping the pressure of the catalytic rectification tower at 1.0MPa, keeping the temperature of the reaction section at the top of the tower at 80 ℃, and ensuring that the molar ratio of the ethylene glycol to the unreacted isobutene is 1.5:1, so that the isobutene in the mixed C4 is fully reacted, the isobutene content in the remaining mixed C4 is less than 0.4 percent, and the isobutene conversion rate is more than 99 percent. And evaporating the residual C4 from the tower top, condensing to obtain the C4 product which is taken out after being etherified. And (3) after the heavy component ethylene glycol mono-tert-butyl ether crude product is subjected to heat exchange and temperature reduction by a heat exchanger, feeding the heavy component ethylene glycol mono-tert-butyl ether crude product into a buffer tank of the ethylene glycol mono-tert-butyl ether crude product to obtain the ethylene glycol mono-tert-butyl ether crude product.
Feeding a part of crude ethylene glycol mono-tert-butyl ether into an ethylene glycol mono-tert-butyl ether lightness-removing tower, and collecting light-component isobutene dimer, tert-butyl alcohol and other by-products under the conditions of rectification pressure of 100KPa and tower top temperature of 70 ℃. And then sending the heavy component at the bottom of the tower into a double ether removing tower, simultaneously adding water with the mass ratio of 1:1 to the ethylene glycol di-tert-butyl ether in the heavy component as an entrainer, and extracting the azeotrope of the ethylene glycol di-tert-butyl ether, the water and the ethylene glycol mono-tert-butyl ether under the conditions that the rectification pressure is 50KPa and the tower top temperature is 50 ℃. And then, sending heavy components at the bottom of the tower into a monoether removing tower, and extracting an ethylene glycol mono-tert-butyl ether product with the content of more than 99% from the side line of the tower under the conditions that the rectification pressure is 20KPa and the temperature at the top of the tower is 100 ℃. The product index parameters are shown in the following table:
preheating a part of crude ethylene glycol mono-tert-butyl ether to 150 ℃ by a preheater, and then cracking raw material feeding mass space velocity is 2.0h at the reaction pressure of 0.1MPa and the reaction temperature of 150 DEG C-1Under the condition ofCarrying out cracking reaction in a tubular reactor filled with a cracking catalyst to generate a mixture of isobutene and ethylene glycol; isobutene in the mixture is separated by an ethylene glycol flash tower, and is purified by an isobutene de-heavy tower to obtain a high-purity isobutene product, wherein the indexes of the high-purity isobutene product are shown in the following table:
| serial number | Name (R) | Detecting the index |
| 1 | Isobutene | 99.94％ |
| 2 | Isobutane | 200ppm |
| 3 | Butene-1 | 5ppm |
| 4 | Cis-buten-2 | 30ppm |
| 5 | Tert-butyl alcohol | 6ppm |
| 6 | Water (W) | 8ppm |
| 7 | Ethylene glycol | 1ppm |
| 8 | Sulfur | 1mg/m3 |
| 9 | Dimer | 9ppm |
Example 5
Fully mixing a mixed C-C raw material with the content of isobutene of 30% and a glycol raw material with the content of 99% purified by a purifier according to the molar ratio of the glycol to the isobutene of 1.5:1, and preheating to 75 ℃ by a preheater; the reaction pressure is 2.0MPa, the reaction temperature is 80 ℃, and the mass space velocity of the ethylene glycol is 2.0h-1Under the reaction condition of (3), the preheated raw material passes through a fixed bed reactor loaded with an etherification catalyst to catalyze isobutene in the mixed C4 to react with ethylene glycol to generate ethylene glycol mono-tert-butyl ether or ethylene glycol di-tert-butyl ether. The isobutene content in the mixed C4 after the reaction in the reaction section is less than 4 percent, and the isobutene conversion rate is more than 90 percent.
Feeding the reaction product into a catalytic rectification tower, feeding the rectified light component mixed C4 into a reaction section filled with an etherification catalyst at the upper part of the tower, continuously reacting unreacted isobutene in the mixed C4 with ethylene glycol under the action of the etherification catalyst, keeping the pressure of the catalytic rectification tower at 1.0MPa, keeping the temperature of the reaction section at the top of the tower at 80 ℃, and ensuring that the molar ratio of the ethylene glycol to the unreacted isobutene is 1.5:1, so that the isobutene in the mixed C4 is fully reacted, the isobutene content in the remaining mixed C4 is less than 0.4 percent, and the isobutene conversion rate is more than 99 percent. And evaporating the residual C4 from the tower top, condensing to obtain the C4 product which is taken out after being etherified. And (3) after the heavy component ethylene glycol mono-tert-butyl ether crude product is subjected to heat exchange and temperature reduction by a heat exchanger, feeding the heavy component ethylene glycol mono-tert-butyl ether crude product into a buffer tank of the ethylene glycol mono-tert-butyl ether crude product to obtain the ethylene glycol mono-tert-butyl ether crude product.
Feeding a part of crude ethylene glycol mono-tert-butyl ether into an ethylene glycol mono-tert-butyl ether lightness-removing tower, and collecting light-component isobutene dimer, tert-butyl alcohol and other by-products under the conditions of rectification pressure of 100KPa and tower top temperature of 70 ℃. And then sending the heavy component at the bottom of the tower into a double ether removing tower, simultaneously adding water with the mass ratio of 1:1 to the ethylene glycol di-tert-butyl ether in the heavy component as an entrainer, and extracting the azeotrope of the ethylene glycol di-tert-butyl ether, the water and the ethylene glycol mono-tert-butyl ether under the conditions that the rectification pressure is 50KPa and the tower top temperature is 50 ℃. And then, sending heavy components at the bottom of the tower into a monoether removing tower, and extracting an ethylene glycol mono-tert-butyl ether product with the content of more than 99% from the side line of the tower under the conditions that the rectification pressure is 20KPa and the temperature at the top of the tower is 100 ℃. The product index parameters are shown in the following table:
preheating a part of crude ethylene glycol mono-tert-butyl ether to 150 ℃ by a preheater, and then cracking raw material feeding mass space velocity of 2.0h at the reaction pressure of 0.1MPa and the reaction temperature of 180 DEG C-1Carrying out cracking reaction through a tubular reactor filled with a cracking catalyst under the condition to generate a mixture of isobutene and ethylene glycol; isobutene in the mixture is separated by an ethylene glycol flash tower, and is purified by an isobutene de-heavy tower to obtain a high-purity isobutene product, wherein the indexes of the high-purity isobutene product are shown in the following table:
Claims (2)
1. a process for producing isobutene and ethylene glycol mono-tert-butyl ether is characterized in that: the production process flow comprises the following steps: an etherification reaction unit, an ethylene glycol mono-tert-butyl ether product unit and an isobutene product unit;
the production process of the etherification reaction unit comprises the following steps: feeding mixed carbon four containing isobutene into a carbon four buffer tank, boosting the pressure of the mixed carbon four feeding pump, and then feeding the mixture into a static mixer to be fully mixed with ethylene glycol; (2) feeding fresh ethylene glycol and recycled ethylene glycol into an ethylene glycol buffer tank, boosting the pressure by an ethylene glycol feed pump, feeding the ethylene glycol into an ethylene glycol purifier, feeding one part of the ethylene glycol without trace impurities into a static mixer to be fully mixed with mixed C4, and feeding the other part of the ethylene glycol into the top of a catalytic rectifying tower to continuously react with unreacted isobutene in an etherification reactor; (3) heating the fully mixed ethylene glycol and mixed C4 by a preheater to a certain temperature, then feeding the heated mixture into a fixed bed etherification reactor, and reacting most of isobutene in the mixed C4 with the ethylene glycol to generate ethylene glycol mono-tert-butyl ether or ethylene glycol di-tert-butyl ether under the action of an etherification catalyst; (4) the reaction product of the etherification reactor enters a catalytic rectification tower, light component mixed carbon four enters a reaction section filled with the etherification catalyst at the upper part of the tower after rectification, unreacted isobutene in the mixed carbon four continuously reacts with ethylene glycol under the action of the etherification catalyst, the remaining carbon four is evaporated out from the top of the tower, the unreacted isobutene is condensed by a circulating condenser and then enters a reflux tank of the catalytic rectification tower, part of condensate is sent to the top of the tower as reflux liquid by a reflux pump of the catalytic rectification tower, and part of carbon four is sold as an etherified carbon four product; after heat exchange and temperature reduction are carried out on the heavy component ethylene glycol mono-tert-butyl ether crude product by a heat exchanger, the heavy component ethylene glycol mono-tert-butyl ether crude product enters a buffer tank of the ethylene glycol mono-tert-butyl ether crude product;
the unit production process of the ethylene glycol mono-tert-butyl ether product comprises the following steps: (1) feeding a part of ethylene glycol tert-butyl ether crude product in an ethylene glycol tert-butyl ether crude product buffer tank into an ethylene glycol tert-butyl ether lightness-removing tower for rectification, and distilling out light components of isobutene dimer and tert-butyl alcohol from the top of the tower; heavy components at the bottom of the tower enter a diether removing tower;
(2) the heavy components at the bottom of the ethylene glycol mono-tert-butyl ether lightness-removing tower enter a double ether removing tower and then form a water-ethylene glycol mono-tert-butyl ether-ethylene glycol double-tert-butyl ether azeotropic system with water entering the tower, and the water-ethylene glycol mono-tert-butyl ether-ethylene glycol double-tert-butyl ether azeotrope is distilled at the top of the tower and then enters a phase separation tank after being condensed; the heavy components at the bottom of the tower enter a glycol mono-tert-butyl ether separation tower; (3) the oil phase in the phase separation tank overflows into an oil phase receiving tank, and the oil phase in the oil phase receiving tank is sent into a cracking reactor for reaction through a discharge pump of the oil phase tank; the water phase enters a water phase receiving tank from the bottom of the phase separation tank, one part of water in the water phase receiving tank enters a diether rectifying tower from the tower through a water phase reflux pump, and the other part of water flows back to the tower from the top of the tower, so that the water is recycled; (4) the heavy components at the bottom of the double ether removal tower enter a single ether removal tower for continuous rectification, and ethylene glycol mono-tert-butyl ether is extracted from the side line of the tower and sent to an ethylene glycol mono-tert-butyl product storage tank to be sold as a product; condensing the light components evaporated from the tower top, feeding a part of the condensed light components into the tower for refluxing, and feeding a part of the condensed light components into a phase splitting tank; sending heavy component ethylene glycol at the bottom of the tower into a recovered ethylene glycol storage tank for recycling;
the isobutene product unit production process comprises the following steps: (1) mixing a crude product of ethylene glycol mono-tert-butyl ether with an oil phase in an oil phase receiving tank, heating the mixture in a preheater of a cracking reactor to a certain temperature, and feeding the mixture into the cracking reactor; under the catalytic action of a cracking catalyst, ethylene glycol mono-tert-butyl ether and ethylene glycol di-tert-butyl ether are subjected to cracking reaction to generate a mixture of ethylene glycol and isobutene; (2) the products of the cracking reactor enter an ethylene glycol flash tower, and light components and heavy components are primarily separated; (3) distilling light components in the ethylene glycol flash tower from the top, then feeding the light components into an isobutene de-heavy tower for rectification and purification, distilling an isobutene product from the top, and sending the isobutene product into an isobutene product storage tank after condensation; the heavy components at the bottom of the tower are sent to an ethylene glycol flash tower for circulation; (4) the heavy components of the ethylene glycol flash tower enter an ethylene glycol light component removal tower to be continuously rectified, the light components are evaporated from the top of the ethylene glycol light component removal tower, and the condensed light components are sent to a byproduct storage tank; feeding heavy components at the bottom of the tower into an ethylene glycol de-heavy tower; (5) the heavy component of the ethylene glycol light component removal tower enters an ethylene glycol heavy component removal tower for continuous rectification, a part of the light component evaporated from the tower top is sent into the tower for reflux after being condensed, the other part of the light component is sent into an ethylene glycol recovery tank for recycling, and the heavy component at the tower bottom is sent into a diethylene glycol product storage tank after being condensed; the production process of the etherification reaction unit comprises the following steps: in the step (1), the content of isobutene in the mixed C4 is 30% -90%, and the step (2): the ethylene glycol purifier is filled with molecular sieve catalystRemoving trace water in the ethylene glycol, and reducing the generation amount of the byproduct tertiary butanol; the step (3): the feeding proportion of the ethylene glycol and the mixed C4 is that the molar ratio of the ethylene glycol to the isobutene in the mixed C4 is 1: 0.5-2; the preheating temperature of the preheater is 30-80 ℃; the etherification reaction temperature is 40-100 ℃; the feeding mass space velocity of the ethylene glycol is 0.5-3.0h-1(ii) a The etherification pressure is 0.5-5.0 Mpa; the conversion rate of isobutene is 80-95%; the etherification reaction catalyst type is one of modified strong acid cation resin catalyst, solid heteropoly acid catalyst, modified molecular sieve catalyst and solid super strong acid catalyst; the step (4): the pressure of the catalytic rectifying tower is 0.5-1.5Mpa, the reaction temperature of the reaction section of the catalytic rectifying tower is 40-100 ℃, and the molar ratio of the glycol to the isobutene of the reaction section of the catalytic rectifying tower is 1: 0.5-2.0; the production process of the ethylene glycol mono-tert-butyl ether product unit comprises the following steps: the temperature of the top of a rectifying tower of the ethylene glycol mono-tert-butyl ether lightness-removing tower in the step (1) is 40-80 ℃, and the rectifying pressure is 10-200 kpa; the mass ratio of the entrainer water to the ethylene glycol di-tert-butyl ether in the step (2) is as follows: 1: 0.1-5.0; the temperature at the top of the tower is 40-80 ℃, and the rectification pressure is 10-100 kpa; the production process of the ethylene glycol mono-tert-butyl ether product unit comprises the following steps: in the step (4), the temperature of the top of the monoether removal tower is 80-150 ℃, and the rectification pressure is 10-100 kpa; the content of ethylene glycol mono-tert-butyl ether product is more than 99 percent, and the content of ethylene glycol is more than 99 percent;
the unit production process of the isobutene product comprises the following steps: in the step (1), the preheating temperature of the cracking reactor is 60-200 ℃, the cracking reaction temperature is 70-150 ℃, the feeding mass space velocity of the cracking raw material is 0.5-3.0h < -1 >, the cracking reaction pressure is 0-0.5MPa, and the type of the cracking reaction catalyst is one of a modified strong-acid cation resin catalyst, a solid heteropoly acid catalyst, a modified molecular sieve catalyst and a solid super strong acid catalyst.
2. The process for producing isobutylene and ethylene glycol mono-t-butyl ether according to claim 1, wherein the step (1) is characterized by: the cracking reactor is of a tubular reactor type.
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| CN109096066B (en) * | 2018-09-29 | 2021-07-30 | 天津科林泰克科技有限公司 | Method and device for removing and recycling ethylene glycol butyl ether in coating wastewater |
| CN109265340B (en) * | 2018-11-19 | 2021-12-17 | 深圳市前海博扬研究院有限公司 | Dihydric alcohol mono-tert-butyl ether carboxylate and preparation method thereof |
| CN111269095B (en) * | 2018-12-04 | 2022-08-12 | 湖南中创化工股份有限公司 | Method and system for refining ethylene glycol tert-butyl ether |
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| CN106748668A (en) * | 2016-11-15 | 2017-05-31 | 潍坊康顺化工有限公司 | Ethylene glycol tertbutyl ether and its production technology |
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