CN110551002A - Method for preparing tert-butyl alcohol by hydrating carbon tetraisobutylene component and preparation system thereof - Google Patents
Method for preparing tert-butyl alcohol by hydrating carbon tetraisobutylene component and preparation system thereof Download PDFInfo
- Publication number
- CN110551002A CN110551002A CN201910964263.7A CN201910964263A CN110551002A CN 110551002 A CN110551002 A CN 110551002A CN 201910964263 A CN201910964263 A CN 201910964263A CN 110551002 A CN110551002 A CN 110551002A
- Authority
- CN
- China
- Prior art keywords
- tower
- carbon
- hydration
- pipeline
- catalytic distillation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application provides a method for preparing tert-butyl alcohol by hydrating a carbon tetraisobutylene component and a preparation system thereof. The preparation system comprises a hydration reactor, a catalytic distillation tower and a tertiary butanol rectifying tower, wherein the hydration reactor is used for carrying out hydration reaction on the carbon tetraisobutylene component, the reaction discharge material enters the lower part of the reaction section of the catalytic distillation tower for continuous reaction, the rectifying section of the tower is connected with an external water replenishing pipeline, and a tower kettle pipeline of the catalytic distillation tower is divided into two branches which are respectively connected to the upper part of the reaction section of the tower and fed back to the hydration reactor; the side line extracted from the stripping section of the catalytic distillation tower is connected to a tertiary butanol rectifying tower, the top pipeline of the tertiary butanol rectifying tower is a tertiary butanol discharging pipeline, and the tower kettle is connected with a drainage pipeline. The invention solves the technical problems of low isobutene hydration conversion rate, complex process and flow and high energy, does not need to add materials to improve the isobutene conversion rate, and has the technical advantages of simple hydration process, short flow, low energy consumption, excellent product index and environment-friendly process.
Description
Technical Field
The patent application relates to a tertiary butanol preparation method and a tertiary butanol preparation system in the field of petrochemical industry, in particular to a method for preparing tertiary butanol by mixing isobutene component of C4 in a hydration manner and a tertiary butanol preparation system.
background
Isobutylene hydration is an important organic hydration reaction. Tert-butyl alcohol is one of important organic chemical raw materials and solvents, and has wide application in the industries of medicine synthesis, rubber synthesis, paint, dye, spice, pesticide and the like. Tert-butanol is obtained mainly by the production process of hydration reaction of isobutylene.
Preparing tert-butyl alcohol acid by isobutene hydration reaction. The existing tertiary butanol production process mainly comprises a sulfuric acid hydration method and an ion exchange resin hydration method. The sulfuric acid hydration method is more traditional, and the method is to use sulfuric acid to esterify isobutene and then hydrolyze the isobutene to produce tert-butyl alcohol, and has the advantages of high conversion rate, long flow, high energy consumption, serious equipment corrosion and generation of a large amount of waste acid, so the method is gradually eliminated and replaces the ion resin hydration method developed in the 70 s. Although the ionic resin hydration method has the advantages of simpler process, less three-waste discharge and basically no equipment corrosion problem, the technical problem of lower conversion rate of isobutene generally exists. Until now, the ionic resin hydration method has been the most important method for producing tertiary butanol at home and abroad.
Over the years, the skilled worker has carried out a lot of research work in improving the isobutene conversion and selectivity of the ionic resin hydration process. For example, patent CN1511814A discloses a method for preparing tert-butyl alcohol, which is to add polyether nonionic surfactant with viscosity average molecular weight of 200-800 in hydration. However, in the non-ionic surfactant 'mixed trace' water, the catalyst pore channel can be quickly blocked by adopting a water circulation process, the service life of the catalyst is influenced, if the water is not recycled, the water resource consumption is huge, and the technical problem that the water purification treatment is difficult exists.
USP4982022 discloses a method for preparing tert-butyl alcohol by catalytic distillation hydration, which is to improve the conversion rate of isobutene by adding a certain amount of water to the upper part of a reaction section of a catalytic distillation tower, but the added water and C4 are mixed poorly, so that the problem of butene polymerization is inevitable.
Patent CN208562191 discloses a device for preparing tert-butyl alcohol by isobutylene hydration, which is provided with three reactors and a carbon four-fractionating tower connected in series, wherein a part of the material in the tower bottom of the carbon four-fractionating tower returns to the first reactor to be used as a solubilizer.
Disclosure of Invention
The invention of the patent application aims to avoid the method for improving the conversion rate of isobutene by adding a solubilizer and the technical problem of high-energy consumption reaction operation caused by the method, and provides a method for preparing tert-butyl alcohol by hydrating a carbon tetraisobutylene component and a preparation system thereof, wherein the method can comprehensively simplify the process, shorten the preparation flow, simplify the system structure and greatly reduce the process wastewater.
The technical scheme of the method for preparing tert-butyl alcohol by hydrating the carbon tetraisobutylene component provided by the application mainly comprises the following technical contents: a method for preparing tert-butyl alcohol by hydrating a carbon tetraisobutylene component comprises the following steps: under the action of a catalyst, mixed carbon four containing isobutene components and raw material water are subjected to hydration reaction in a hydration reactor, a reaction discharge pipeline enters the lower part of a reaction section of a catalytic distillation tower, the hydration reaction is continued under the action of the catalyst in the tower, the residual carbon four is output from the top of the tower, a rectifying section of the catalytic distillation tower is connected with an external water replenishing pipeline and is coupled in the tower to form water extraction treatment for separating tert-butyl alcohol, tower bottom materials of the catalytic distillation tower are divided into two paths, one path is a supplementary branch connected to the upper part of the reaction section of the catalytic distillation tower, and the other path is a circulating branch with the feeding connected to the hydration; the side material of the stripping section of the catalytic distillation tower enters a tertiary butanol rectifying tower, tertiary butanol separated by the tertiary butanol rectifying tower is discharged from a tower top pipeline, and separated water is discharged from a tower kettle.
In a preferable technical means of the integral technical scheme, a reaction discharge pipeline of the hydration reactor enters the lowest part of the reaction section of the catalytic distillation tower.
In a preferred technical means of the integral technical scheme, the supplementary branch is connected to the uppermost part of the reaction section of the catalytic distillation tower.
One of the whole technical schemes is optimized, and the hydration reaction process conditions of the parallel flow type hydration reactor are that the inlet temperature of the raw material is 50-60 ℃, the pressure is 0.8-2.0 Mpa, the space velocity of carbon four is 0.2-0.6 h ～1, and the volume ratio of the desalted water to the carbon four is (1-2): 1.
One preferable technical means of the whole technical scheme is that the hydration reaction process conditions of the counter-flow type hydration reactor are that the temperature of a catalyst bed layer is 70-80 ℃, the pressure is 0.8-2.0 Mpa, the space velocity of carbon four is 0.2-0.6 h ～1, and the feeding volume ratio of desalted water to carbon four is 1-2: 1.
One preferable technical means of the whole technical scheme is that the reaction process conditions of the catalytic distillation tower are as follows: the pressure is 0.6-0.8 Mpa, the reflux ratio is (1-2): 1, the tower top temperature is 55-65 ℃, the volume ratio of the desalted water amount of the external water replenishing pipeline 11 to the carbon four feeding amount is (0.5-1): 1, and the volume ratio of the circulating amount of the circulating branch to the carbon four feeding amount is (0.2-0.4): 1.
One preferable technical means of the whole technical scheme is that the process conditions of the tertiary butanol rectifying tower are as follows: the normal pressure, the reflux ratio (1-3) is 1, and the tower top temperature is 85-90 ℃.
The application also provides a preparation system for preparing tert-butyl alcohol by hydrating the carbon tetraisobutylene component, the preparation system comprises a hydration reactor, a catalytic distillation tower and a tert-butyl alcohol rectifying tower, a reaction discharge pipeline of the hydration reactor is connected to the lower part of a reaction section of the catalytic distillation tower, the top of the catalytic distillation tower is connected with a residual carbon four output pipeline, the rectifying section of the tower is connected with an external water replenishing pipeline, a tower kettle pipeline is divided into two branches, one branch is connected to the upper part of the reaction section of the tower for replenishing, and the other branch is fed and returned to the hydration reactor for a circulating branch; the side line extracted from the stripping section of the catalytic distillation tower is connected to a tertiary butanol rectifying tower, the top pipeline of the tertiary butanol rectifying tower is a tertiary butanol discharging pipeline, and the tower kettle is connected with a drainage pipeline.
One preferable technical means of the whole technical scheme is that the hydration reactor is a concurrent flow reactor, the mixed carbon four and the raw material water are mixed by the mixer and are connected to enter a feeding pipe at the top of the hydration reactor, and the circulating branch is returned to the feeding end of the mixer.
In a preferred embodiment of the above overall technical solution, the hydration reactor is a reverse-flow reactor, the lower part of the catalyst of the hydration reactor is connected to a mixed carbon four pipeline, the upper part of the hydration reactor is connected to a raw material water pipeline at the water phase layer of the raw material water and mixed carbon four layer section, and the circulation branch is connected back to the uppermost part of the catalyst of the hydration reactor.
The technical scheme of the preparation system for preparing tert-butyl alcohol by hydrating the carbon tetraisobutylene component disclosed by the application has the technical advantages of simple hydration process, short flow, low energy consumption, excellent product index and environment-friendly process. The preparation system is formed by serially connecting a hydration reactor, a catalytic distillation tower and a tertiary butyl alcohol rectifying tower, residual isobutene in the discharged material of the reactor is continuously subjected to hydration reaction to generate tertiary butyl alcohol, carbon four is separated from a tertiary butyl alcohol aqueous solution in the tower, and the extraction of the tertiary butyl alcohol is completed in the tertiary butyl alcohol rectifying tower, wherein the rectifying section of the catalytic distillation tower receives external water supplement, the catalytic distillation tower is coupled with a tertiary butyl alcohol water extraction process, the content of the tertiary butyl alcohol in the carbon four product is reduced, the quality of the carbon four product is improved, and meanwhile, the balance of isobutene hydration reaction is broken by using the external water supplement, so that the isobutene is deeply converted, and the isobutene conversion rate is improved; in addition, the feeding of the tertiary butanol rectifying tower is from a side line extracted from a stripping section of the catalytic distillation tower, and a tertiary butanol enrichment area is formed by azeotropy of tertiary butanol and water at the stripping section, so that the operation load of the tertiary butanol rectifying tower is greatly reduced, the feeding amount of the tertiary butanol rectifying tower is reduced, and the operation energy consumption is effectively reduced; a pipeline is led out from the tower kettle of the catalytic distillation tower, one part of the pipeline is led to a hydration reactor for feeding, and the other part of the pipeline is led to the upper part of a reaction section of the catalytic distillation tower, so that the content of the tertiary butyl alcohol in the tertiary butyl alcohol aqueous solution led out is low and is only 2-4 percent, the temperature is high, the emulsification is good, the tertiary butyl group of the tertiary butyl alcohol is lipophilic, and the hydroxyl group is hydrophilic, the intersolubility of raw material water and carbon four can be effectively improved, the contact between isobutene and the raw material water is increased, the conversion rate of isobutene is improved, the occurrence of side reactions is avoided, the generation of dimer and polymer impurities is inhibited, and the circulating water does not contain polymers generated by the side reactions, so the technical problem that the catalyst is blocked due to the existence of the polymers in the water recycling is solved, the service cycle of the catalyst is effectively prolonged, the; fourthly, the drainage of the drainage pipeline of the tower kettle of the tertiary butanol rectification tower can be used as supplementary and cyclic utilization of raw material water, the redundant part is easy to purify and discharge in an environment-friendly way, the conversion rate of the isobutene of the hydration reactor can reach over 75 percent by the technical scheme, and the conversion rate of the isobutene can be further improved to over 90 percent by the catalytic distillation tower. Therefore, the water resource consumption is further reduced, and the technical advantage of environment-friendly emission of water resources is achieved.
Drawings
FIGS. 1 and 2 are views showing two embodiments of a system for producing the present patent application.
Detailed Description
The method for preparing the tertiary butanol by hydrating the carbon tetraisobutylene component is realized based on a preparation system thereof.
The system for preparing the tertiary butanol by hydrating the carbon tetraisobutylene component comprises a hydration reactor 3, a catalytic distillation tower 4 and a tertiary butanol rectifying tower 5. In this embodiment, the hydration reactor 3 is a fixed reaction bed filled with a strongly acidic resin catalyst such as DT-012 type catalyst or DT-017 resin catalyst manufactured by Dandeng Zhu Special resin Co. The catalytic distillation column 4 is packed with modular catalyst. Specifically, a CDM-142 type module of special resin Co., Ltd, Dandong Mingzhu, is selected and a DT-012 type catalyst or a DT-017 type resin catalyst is filled in the module.
FIG. 1 shows a hydration reaction connection structure of mixed C4 and raw material water fed in parallel, wherein a mixed C1 pipeline containing isobutene and a raw material water pipeline 2 are mixed by a mixer 12, preheated to the reaction temperature of a hydration reactor 3, and fed into the hydration reactor 3, the raw material water comprises external water supplement which is preferably desalted water, the reaction conditions of the hydration reactor 3 are that the inlet temperature of the raw material is 50-60 ℃, the pressure is 0.8-2.0 Mpa, the space velocity of C4 is 0.2-0.6 h ～1, the volume ratio of the desalted water to C4 is (1-2): 1, and isobutene of C4 is hydrated to generate tert-butyl alcohol under the action of a catalyst.
The reaction outlet line 13 of the hydration reactor 3 is connected to the lowermost part of the reaction section of the catalytic distillation column 4. The top of the catalytic distillation tower 4 is connected with a residual carbon four output pipeline 8. The kettle pipeline of the catalytic distillation tower 4 is divided into two paths, one path is a supplementary branch 7 connected to the uppermost part of the reaction section of the tower, the other path is a feeding end of a mixer 12 returned to by a circulating branch 6, and the rectifying section of the catalytic distillation tower 4 is connected with an external water supplementing pipeline 11. The process operating conditions of the catalytic distillation column 4 are: the pressure is 0.6-0.8 Mpa, the reflux ratio is (1-2): 1, the temperature at the top of the tower is 55-65 ℃, the volume ratio of the circulating amount of the circulating branch 6 to the carbon four fed material is (0.2-0.4): 1, the tertiary butanol aqueous solution led out from the tower bottom of the catalytic distillation tower 4 has low tertiary butanol content, the concentration is only 2-4 percent, the emulsification is good along with higher temperature, the lipophilic tertiary butyl and hydrophilic hydroxyl of the tertiary butanol can greatly improve the intersolubility of raw material water and carbon four, thereby enhancing the contact performance of isobutene and raw material water, promoting isobutene reaction, improving isobutene conversion rate, simultaneously avoiding the generation of side reaction and inhibiting the generation of dimer and polymer impurities, leading the circulating water of the circulating branch 6 and the supplementing water of the supplementing branch 7 to contain no side reaction polymer product, ensuring that the catalyst is not blocked due to the existence of the polymer when the water is recycled, and effectively prolonging the service cycle of the catalyst, and the additional consumption of water resources is reduced. The volume ratio of the desalted water amount of the external water replenishing pipeline 11 to the carbon four feeding amount is (0.5-1): 1. The external water supplement enters a rectifying section of the catalytic distillation tower 4, which is equivalent to a tertiary butanol water extraction process coupled in the catalytic distillation tower, so that the content of tertiary butanol in the carbon four product is reduced, the quality of the carbon four product is improved, more importantly, the external water supplement is utilized to break the hydration reaction balance of isobutene, the deep conversion of isobutene is promoted, and the conversion rate of isobutene is improved.
A side line 14 extracted from the stripping section of the catalytic distillation column 4 is connected to a tertiary butanol rectifying column 5. The operation conditions of the tertiary butanol rectification column 4 are as follows: the normal pressure and the reflux ratio (1-3) are 1, the temperature at the top of the tower is 85-90 ℃, a pipeline 9 at the top of the tower is a tertiary butanol discharging pipeline, and a drainage pipeline 10 is connected with the bottom of the tower.
FIG. 2 shows a hydration reaction connection structure of mixed C4 and raw material water fed by a countercurrent method, the system structure of a catalytic distillation tower 4 and a tertiary butanol rectification tower 5 is the same as that of FIG. 1. a mixed C four pipeline 1 containing isobutene is connected to the lower part of a catalyst of a hydration reactor 3, a raw material water pipeline 2 is connected to a water phase layer of a water and carbon four-layer section at the upper part of the hydration reactor 3, the raw material water comprises external water supplemented with desalted water, and the hydration reactor 3 is preferably filled with a temperature-resistant strong acid resin catalyst, such as DT-DT catalyst produced by Dandong Mingzhu Special resin Co., Ltd.the reaction conditions of the hydration reactor 3 are that the catalyst bed temperature is 70-80 ℃, the pressure is 0.8-2.0 MPa, the space velocity of C four is 0.2-0.6 h ～1, and the feeding volume ratio of desalted water to C four is 1-2: 1.
the reaction discharge of the hydration reactor 3 is connected to the lowest part of the reaction section of the catalytic distillation tower 4 through a reaction discharge pipeline 13 according to the process conditions: the pressure is 0.6-0.8 Mpa, the reflux ratio is 1-2: 1, the temperature at the top of the tower is 55-65 ℃, and the reaction is continued in the catalytic distillation tower 4. The catalytic distillation tower 4 is filled with a modular catalyst, such as a CDM-142 module of Dandong Mingzhu special resin Co., Ltd, and the module is preferably filled with a temperature-resistant strong acid catalyst, such as a DT-017 module of Dandong Mingzhu special resin Co., Ltd.
The top of the catalytic distillation tower 4 is connected with a residual carbon four output pipeline 8, the tower kettle pipeline is divided into two paths, one path is a supplementary branch 7 connected to the uppermost part of the reaction section of the tower, the other path is a circulating branch 6 returned to the uppermost part of the catalyst of the hydration reactor 3, and the volume ratio of the circulating amount of the circulating branch 6 to the carbon four feeding is (0.2-0.4): 1; the tertiary butanol aqueous solution led out from the tower kettle of the catalytic distillation tower 4 has low tertiary butanol content, the concentration is only 2-4%, and the emulsification is better along with higher temperature, the oleophylic tertiary butyl and hydrophilic hydroxyl of the tertiary butanol can greatly improve the intersolubility of raw material water and carbon four, thereby enhancing the contact performance of isobutene and the raw material water, promoting isobutene reaction, improving isobutene conversion rate, simultaneously avoiding the occurrence of side reaction, inhibiting the generation of dimer and polymer impurities, leading the circulating water of the circulating branch 6 and the supplementing water of the supplementing branch 7 not to contain side reaction polymer products, ensuring that the catalyst is not blocked by the existence of the polymer when the water is recycled, effectively prolonging the service cycle of the catalyst, and reducing the additional consumption of water resources. The rectifying section of the catalytic distillation tower 4 is connected with an external water replenishing pipeline 11, and the volume ratio of the desalted water and the carbon four feed of the external water replenishing pipeline 11 is (0.5-1): 1. The external water supplement enters a rectifying section of the catalytic distillation tower 4, which is equivalent to a tertiary butanol water extraction process coupled in the catalytic distillation tower, so that the content of tertiary butanol in the carbon four product is reduced, the quality of the carbon four product is improved, more importantly, the external water supplement is utilized to break the hydration reaction balance of isobutene, the deep conversion of isobutene is promoted, and the conversion rate of isobutene is improved.
A side line 14 extracted from the stripping section of the catalytic distillation column 4 is connected to a tertiary butanol rectifying column 5. The operation conditions of the tertiary butanol rectification column 4 are as follows: the normal pressure and the reflux ratio (1-3) are 1, the temperature at the top of the tower is 85-90 ℃, a pipeline 9 at the top of the tower is a tertiary butanol discharging pipeline, and a drainage pipeline 10 is connected with the bottom of the tower.
Example 1
Taking the catalytic cracking carbon four cocurrent hydration production of tertiary butanol in an oil refinery as an example, the content of the cracked carbon four isobutene in the following examples 2 and 3 is 17.39 percent.
The hydration reactor 3 is filled with DT-012 resin catalyst, the process conditions are that the inlet temperature is 50 ℃, the pressure is 0.8Mpa, the carbon four space velocity is 0.2h ～1, the volume ratio of the desalted water feeding material to the carbon four feeding material is 1:1, the volume ratio of the circulation branch 6 to the carbon four feeding material is 0.2:1, the volume ratio of the desalted water amount of the external water replenishing pipeline 11 to the carbon four feeding material is 0.5:1, the catalytic distillation tower is filled with a modular catalyst, the type of the modular catalyst is CDM-142, the DT-012 type catalyst is filled, the process conditions of the catalytic distillation tower 4 are that the pressure is 0.6Mpa, the reflux ratio is 1:1, the tower top temperature is 55 ℃, the operation conditions of the tertiary butanol rectification tower are that the reflux ratio is 1:1, and the tower top temperature is 85 ℃.
Actual operation detection shows that residual carbon four with the tertiary butanol content of 193ppm is obtained at the top of the catalytic distillation tower 4, and a tertiary butanol product with the mass content of 87.3 percent is obtained at a top pipeline 9 of the tertiary butanol rectifying tower. The isobutene conversion of the hydration reactor 3 was 72.5%, the total isobutene conversion was 92.4%, and the tert-butanol selectivity was 99.2%.
Example 2:
The hydration reactor 3 is filled with a cylindrical granular DT-012 resin catalyst, the process conditions are that the inlet temperature is 60 ℃, the pressure is 2.0Mpa, the space velocity of carbon four is 0.6h ～1, the volume ratio of the desalted water feeding material to the carbon four feeding material is 2:1, the volume ratio of the circulation branch 6 to the carbon four feeding material is 0.4:1, the volume ratio of the desalted water amount of the external water replenishing pipeline 11 to the carbon four feeding material is 1:1, the catalytic distillation tower is filled with a modular catalyst, the module type of the modular catalyst is CDM-142, the DT-012 type catalyst is filled, the process conditions of the catalytic distillation tower 4 are that the pressure is 0.8Mpa, the reflux ratio is 2:1, the tower top temperature is 65 ℃, the operation conditions of the tertiary butanol rectification tower are normal pressure, the reflux ratio is 3:1 and the tower top temperature is 90 ℃.
Actual operation detection shows that residual carbon four with the tertiary butanol content of 127ppm is obtained at the top of the catalytic distillation tower 4, and a tertiary butanol product with the mass content of 86.9 percent is obtained at the top pipeline 9 of the tertiary butanol rectifying tower. The conversion of isobutene in the hydration reactor 3 was 71.9%, the total conversion of isobutene was 92.7%, and the selectivity to tert-butanol was 99.6%.
Example 3:
The hydration reactor 3 is filled with Raschig annular DT-012 resin catalyst, the technological reaction conditions are that the inlet temperature is 55 ℃, the pressure is 1.2Mpa, the carbon four space velocity is 0.4h ～1, the volume ratio of the desalted water feed to the carbon four feed is 1.2:1, the volume ratio of the circulation branch 6 to the carbon four feed is 0.3:1, the volume ratio of the desalted water amount of the external water replenishing pipeline 11 to the carbon four feed is 0.7:1, the catalytic distillation tower is filled with a modular catalyst, the module type of the modular catalyst is CDM-142, the DT-012 type catalyst is filled, the technological conditions of the catalytic distillation tower 4 are that the pressure is 0.7Mpa, the reflux ratio is 1.5:1, the tower top temperature is 61 ℃, the operation conditions of the tertiary butanol rectification tower are normal pressure, the reflux ratio is 2:1, and the tower top temperature is 87 ℃.
Actual operation detection shows that the residual carbon four product with the tertiary butanol content of 256ppm is obtained at the top of the catalytic distillation tower 4, and the tertiary butanol product with the mass content of 86.7 percent is obtained at the top pipeline 9 of the tertiary butanol rectifying tower 5. The conversion of isobutene in the hydration reactor 3 was 71.9%, the total conversion of isobutene was 92.1%, and the selectivity to tert-butanol was 99.3%.
Example 4:
Taking the example of the countercurrent hydration of the cracked raffinate carbon four to produce the tertiary butanol, the carbon four feeds of the following examples are the same, and are the carbon four with the isobutene content of 41.67 percent.
a catalyst DT-017 type of special resin Limited company of Dandong Mingzhu is selected to be filled in a hydration reactor 3, a modularized catalyst is filled in a catalytic distillation tower 4, the type of the module selects CDM-142, the DT-017 type catalyst is filled in the catalyst, but the selected catalyst is not limited, a mixed carbon four pipeline 1 is connected to the lower part of the catalyst of the hydration reactor 3, a raw material water pipeline 2 is connected to a water phase layer of a water and carbon four-layer section at the upper part of the hydration reactor 3, the process conditions of the hydration reactor 3 are that the temperature of a catalyst bed layer is 70 ℃, the pressure is 0.8Mpa, the carbon four airspeed is 0.2h ～1, the volume ratio of a desalted water feed to a carbon four feed is 1:1, the volume ratio of a circulation branch 6 to the carbon four feed is 0.2:1, the volume ratio of the desalted water amount of an external water supplementing pipeline 11 to the carbon four feed is 0.5:1, the process conditions of the catalytic distillation tower 4 are that the pressure is 0.6Mpa, the reflux ratio is 1:1, the tower top temperature is 55 ℃, the operation conditions of the tertiary butanol rectification tower top.
Actual operation detection shows that residual carbon four products with the tertiary butanol content of 287ppm are obtained at the top of the catalytic distillation tower 4, and tertiary butanol products with the mass content of 87.3% are obtained through a tertiary butanol rectifying tower top pipeline 9. The conversion of isobutylene in the hydration reactor 3 was 72.7%, the total conversion of isobutylene was 92.6%, and the selectivity of t-butanol was 99.1%.
Example 5:
A DT-017 type catalyst filled with cylindrical particles of special resin Limited company Dandong Mingzhu is selected from a hydration reactor 3, a modularized catalyst is filled in a catalytic distillation tower 4, the type of the module selects CDM-142, the DT-017 type catalyst is filled in the CDM-142, a mixed carbon four pipeline 1 is connected to the lower part of the catalyst of the hydration reactor 3, a raw material water pipeline 2 is connected to a water phase layer of a water and carbon four-layer section at the upper part of the hydration reactor 3, the process conditions of the hydration reactor 3 are that the temperature of a catalyst bed layer is 80 ℃, the pressure is 2.0Mpa, the space velocity of carbon four is 0.6h ～1, the volume ratio of a desalted water feed to the carbon four feed is 2:1, the volume ratio of a circulating branch 6 to the carbon four feed is 0.4:1, the volume ratio of the desalted water feed to the carbon four feed of an external water pipeline 11 is 1:1, the process conditions of the catalytic distillation tower 4 are that the pressure is 0.8Mpa and the reflux ratio is 2:1, the tower top temperature is 65 ℃.
Actual operation detection shows that residual carbon four products with the tertiary butanol content of 193ppm are obtained at the top of the catalytic distillation tower 4, and tertiary butanol products with the mass content of 87.8 percent are obtained through a tertiary butanol rectifying tower top pipeline 9. The isobutene conversion of the hydration reactor 3 was 73.6%, the total isobutene conversion was 91.8%, and the tert-butanol selectivity was 99.2%.
Example 6:
A catalyst DT-017 type of special resin Limited company of Dandong Mingzhu is selected from a hydration reactor 3 and is crushed into a wheel shape and is filled in the hydration reactor 3, a modular catalyst is filled in a catalytic distillation tower 4, the modular type of the catalyst selects CDM-142 and is filled with the catalyst DT-017 type, a mixed carbon four pipeline 1 is connected to the lower part of the catalyst of the hydration reactor 3, a raw material water pipeline 2 is connected to a water phase layer of a water and carbon four-layer section at the upper part of the hydration reactor 3, the hydration reactor 3 carries out hydration reaction under the following process conditions that the temperature of a catalyst bed layer is 75 ℃, the pressure is 1.5Mpa, the space velocity of carbon four is 0.5h ～1, the volume ratio of a desalted water feed to a carbon four feed is 1.3:1, the volume ratio of a circulation branch 6 to the carbon four feed is 0.3:1, the volume ratio of a desalted water feed to the carbon four feed of an external water supply pipeline 11 to the carbon four feed is 0.7:1, the process conditions that the pressure is 0.7Mpa, the temperature of a circulation branch 6: 1, the temperature of a reflux temperature of a tower top and the reflux temperature of a rectifying tower top are 1.6: 61 ℃.
Actual operation detection shows that residual carbon four products with the tertiary butanol content of 193ppm are obtained at the top of the catalytic distillation tower 4, and tertiary butanol products with the mass content of 87.8 percent are obtained through a tertiary butanol rectifying tower top pipeline 9. The isobutene conversion of the hydration reactor 3 was 71.7%, the total isobutene conversion was 93.1%, and the tert-butanol selectivity was 99.3%.
Claims (10)
1. A method for preparing tert-butyl alcohol by hydrating a carbon tetraisobutylene component comprises the following steps: under the action of a catalyst, mixed carbon four containing isobutene components and raw material water are subjected to hydration reaction in a hydration reactor, a reaction discharge pipeline enters the lower part of a reaction section of a catalytic distillation tower, the hydration reaction is continued under the action of the catalyst in the tower, and residual carbon four is output from the top of the tower; the side material of the stripping section of the catalytic distillation tower enters a tertiary butanol rectifying tower, tertiary butanol separated by the tertiary butanol rectifying tower is discharged from a tower top pipeline, and separated water is discharged from a tower kettle.
2. The method for preparing tert-butyl alcohol by hydration of carbon tetraisobutylene component as claimed in claim 1, wherein the reaction outlet line of the hydration reactor enters the lowermost part of the reaction section of the catalytic distillation column.
3. The method for preparing tert-butyl alcohol by hydration of carbon tetraisobutylene as claimed in claim 1, wherein a supplementary branch is connected to an uppermost portion of the reaction section of the catalytic distillation column.
4. The method for preparing tert-butyl alcohol by hydration of the carbon-tetraisobutylene component according to claim 1, 2 or 3, wherein the hydration reaction process conditions of the parallel flow type hydration reactor are that the inlet temperature of the raw material is 50-60 ℃, the pressure is 0.8-2.0 Mpa, the space velocity of carbon-tetrad is 0.2-0.6 h ～1, and the volume ratio of the desalted water to the carbon-tetrad is (1-2): 1.
5. The method for preparing tert-butyl alcohol by hydration of the carbon-tetraisobutylene component according to claim 1, 2 or 3, wherein the hydration reaction process conditions of the counter-flow type hydration reactor are that the temperature of a catalyst bed is 70-80 ℃, the pressure is 0.8-2.0 Mpa, the space velocity of carbon-tetrad is 0.2-0.6 h ～1, and the feeding volume ratio of desalted water to carbon-tetrad is 1-2: 1.
6. The method for preparing tert-butyl alcohol by hydration of carbon tetraisobutylene component as claimed in claim 1, 2 or 3, wherein the reaction process conditions of the catalytic distillation column are as follows: the pressure is 0.6-0.8 Mpa, the reflux ratio is (1-2): 1, the tower top temperature is 55-65 ℃, the volume ratio of the desalted water amount of the external water replenishing pipeline 11 to the carbon four feeding amount is (0.5-1): 1, and the volume ratio of the circulating amount of the circulating branch to the carbon four feeding amount is (0.2-0.4): 1.
7. The method for preparing tert-butyl alcohol by hydrating carbon tetraisobutylene component according to claim 1, 2 or 3, wherein the process conditions of the tert-butyl alcohol rectifying column are as follows: the normal pressure, the reflux ratio (1-3) is 1, and the tower top temperature is 85-90 ℃.
8. A preparation system for preparing tertiary butanol by hydrating carbon tetraisobutylene components according to any one of claims 1 to 7, which is characterized by comprising a hydration reactor (3), a catalytic distillation tower (4) and a tertiary butanol rectification tower (5), wherein a reaction discharge pipeline of the hydration reactor (5) is connected to the lower part of a reaction section of the catalytic distillation tower (4), the top of the catalytic distillation tower is connected with a residual carbon four output pipeline (8), the rectification section of the tower is connected with an external water replenishing pipeline (11), a tower kettle pipeline is divided into two branches, one branch is a replenishing branch (7) which is connected to the upper part of the reaction section of the tower, and the other branch is a circulating branch (6) which is fed and returned to the hydration reactor; the side line extracted from the stripping section of the catalytic distillation tower is connected to a tertiary butanol rectifying tower (5), the top pipeline (9) of the tertiary butanol rectifying tower is a tertiary butanol discharging pipeline, and the tower kettle is connected with a drainage pipeline (10).
9. The system for preparing tert-butyl alcohol by hydration of carbon tetraisobutylene as claimed in claim 8, wherein the hydration reactor is a concurrent flow reactor, the mixed carbon tetraisobutylene and the raw water are mixed by a mixer (12) and are connected to a feeding pipe at the top of the hydration reactor, and the circulating branch (6) is returned to the feeding end of the mixer.
10. The system for preparing tert-butanol by hydration of carbon tetraisobutylene as claimed in claim 8, wherein the hydration reactor is a reverse flow reactor, the lower part of the catalyst of the hydration reactor is connected with a mixed carbon four line (1), the upper part of the hydration reactor is connected with a raw material water line (2) at the water phase layer of the raw material water and mixed carbon four layer section, and the circulation branch (6) is connected back to the uppermost part of the catalyst of the hydration reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910964263.7A CN110551002B (en) | 2019-10-11 | 2019-10-11 | Method and system for preparing tertiary butanol by hydration of carbon tetraisobutene component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910964263.7A CN110551002B (en) | 2019-10-11 | 2019-10-11 | Method and system for preparing tertiary butanol by hydration of carbon tetraisobutene component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110551002A true CN110551002A (en) | 2019-12-10 |
| CN110551002B CN110551002B (en) | 2023-10-13 |
Family
ID=68742862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910964263.7A Active CN110551002B (en) | 2019-10-11 | 2019-10-11 | Method and system for preparing tertiary butanol by hydration of carbon tetraisobutene component |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110551002B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115724714A (en) * | 2021-08-26 | 2023-03-03 | 中国石油化工股份有限公司 | Synthesis method of tert-amyl alcohol |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982022A (en) * | 1989-08-28 | 1991-01-01 | Chemical Research & Licensing Company | Process for the preparation of tertiary alcohols |
| CN1511815A (en) * | 2002-12-31 | 2004-07-14 | 中国石化集团齐鲁石油化工公司 | Process for preparing tertiary butanol |
| CN1511814A (en) * | 2002-12-31 | 2004-07-14 | 中国石化集团齐鲁石油化工公司 | Process for preparing tertiary butanol |
| US20060025638A1 (en) * | 2002-12-24 | 2006-02-02 | Oxeno Olefinchemie Gmbh | Method for producing tert butanol by means of reactive rectification |
| CN101423454A (en) * | 2007-11-01 | 2009-05-06 | 中国石油天然气股份有限公司 | Method for preparing tert-butyl alcohol by reaction extraction of carbon-tetrahydrocarbon containing isobutene |
| CN102633588A (en) * | 2012-03-30 | 2012-08-15 | 北京化工大学 | Method for preparing high-purity isobutene from raffinate C4 by means of separation |
| CN105130741A (en) * | 2015-10-13 | 2015-12-09 | 宁波金海晨光化学股份有限公司 | Method for preparing isoprene by means of reaction and distillation |
| CN109824475A (en) * | 2019-04-09 | 2019-05-31 | 烟台大学 | A method of utilizing the isobutene hydration production tert-butyl alcohol in mixing carbon four |
-
2019
- 2019-10-11 CN CN201910964263.7A patent/CN110551002B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982022A (en) * | 1989-08-28 | 1991-01-01 | Chemical Research & Licensing Company | Process for the preparation of tertiary alcohols |
| US20060025638A1 (en) * | 2002-12-24 | 2006-02-02 | Oxeno Olefinchemie Gmbh | Method for producing tert butanol by means of reactive rectification |
| CN1511815A (en) * | 2002-12-31 | 2004-07-14 | 中国石化集团齐鲁石油化工公司 | Process for preparing tertiary butanol |
| CN1511814A (en) * | 2002-12-31 | 2004-07-14 | 中国石化集团齐鲁石油化工公司 | Process for preparing tertiary butanol |
| CN101423454A (en) * | 2007-11-01 | 2009-05-06 | 中国石油天然气股份有限公司 | Method for preparing tert-butyl alcohol by reaction extraction of carbon-tetrahydrocarbon containing isobutene |
| CN102633588A (en) * | 2012-03-30 | 2012-08-15 | 北京化工大学 | Method for preparing high-purity isobutene from raffinate C4 by means of separation |
| CN105130741A (en) * | 2015-10-13 | 2015-12-09 | 宁波金海晨光化学股份有限公司 | Method for preparing isoprene by means of reaction and distillation |
| CN109824475A (en) * | 2019-04-09 | 2019-05-31 | 烟台大学 | A method of utilizing the isobutene hydration production tert-butyl alcohol in mixing carbon four |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115724714A (en) * | 2021-08-26 | 2023-03-03 | 中国石油化工股份有限公司 | Synthesis method of tert-amyl alcohol |
| CN115724714B (en) * | 2021-08-26 | 2024-05-17 | 中国石油化工股份有限公司 | Synthesis method of tertiary amyl alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110551002B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109369319B (en) | Method for maximizing production of propylene by taking C4-C8 olefin as raw material | |
| CN107827694B (en) | Device and method for producing isooctane by adopting indirect alkylation technology | |
| CN104250205B (en) | The preparation method of methyl tertiary butyl ether and device thereof | |
| CN109012504B (en) | Method for preparing raw material by preparing high-content butene-1 from carbon four by co-production method and system device thereof | |
| CN105272941A (en) | Propylene oxide production method | |
| CN104478644B (en) | A kind of tert-butyl alcohol is prepared the method for isobutene | |
| CN100519704C (en) | Catalytic cracking method for producing more propylene | |
| CN109369318B (en) | Method for maximizing production of propylene by using C5 olefin as main raw material | |
| CN103880781A (en) | Continuous production method for preparing cyclohexene oxide through cyclohexene oxidation with hydrogen peroxide under normal pressure | |
| CN108002995A (en) | A kind of method and its equipment of acetone two-step method synthesizing methyl isobutyl ketone | |
| CN110551002A (en) | Method for preparing tert-butyl alcohol by hydrating carbon tetraisobutylene component and preparation system thereof | |
| CN108774100A (en) | A kind of tert-butyl alcohol and methanol prepare the integrated processes of methyl tertiary butyl ether(MTBE) and isobutene | |
| CN112079799A (en) | Process for preparing maleic anhydride and phthalic anhydride by oxidizing n-pentane | |
| CN110483282B (en) | Device and method for producing high-concentration ethylene glycol diacetate | |
| CN105439792B (en) | The method of the refined propylene of recovery | |
| CN104672046B (en) | Method of increasing ethylene and propylene yields by freshening C-4 olefins in catalytic cracking or pyrolysis process after separation | |
| CN101423454B (en) | Method for preparing tert-butyl alcohol by reaction extraction of carbon-tetrahydrocarbon containing isobutene | |
| CN210736610U (en) | Preparation system for preparing tert-butyl alcohol by hydration of carbon tetraisobutylene component | |
| CN109956845A (en) | A kind of propylene polymerization prepares the process of nonene | |
| CN202465559U (en) | Combined device for producing methyl tertiary butyl ether (MTBE) by utilizing mixed carbon 4 (C4) | |
| CN105315238A (en) | Production equipment of epoxypropane | |
| CN210825991U (en) | Device capable of providing carbon four raw materials for MTBE downstream device | |
| CN106520187B (en) | Light gasoline hydrocarbon recombination etherification catalytic rectification process and device thereof | |
| CN104250204A (en) | Mixing etherification technology | |
| CN210560292U (en) | Device for preparing methanol gasoline blending component by using waste chemical raw materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |