CN110776389B - Compound catalyst and method for preparing styrene - Google Patents
Compound catalyst and method for preparing styrene Download PDFInfo
- Publication number
- CN110776389B CN110776389B CN201911201679.XA CN201911201679A CN110776389B CN 110776389 B CN110776389 B CN 110776389B CN 201911201679 A CN201911201679 A CN 201911201679A CN 110776389 B CN110776389 B CN 110776389B
- Authority
- CN
- China
- Prior art keywords
- styrene
- catalyst
- dehydration
- inhibitor
- sulfonic acid
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- 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
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
- C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
- C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
- C07C15/46—Styrene; Ring-alkylated styrenes
Abstract
The invention discloses a method for preparing styrene, wherein 1-phenethyl alcohol is dehydrated to generate styrene in the presence of a complex catalyst formed by compounding methane sulfonic acid with one or two of p-methoxyphenol and p-phenol formic acid inhibitors. The composite catalyst and the preparation method of styrene can realize the respective circulation of the dehydration catalyst and the side reaction inhibitor, the total dosage of the composite catalyst is low, the generation of byproducts is reduced, the conversion rate is improved, and the selectivity of the styrene can reach more than 98.5 percent.
Description
Technical Field
The invention relates to a compound catalyst for preparing styrene and a method thereof, in particular to a method for preparing styrene from a raw material containing 1-phenethyl alcohol through an external circulation reaction and rectification.
Background
Styrene is an important basic organic chemical raw material and is mainly used for producing polystyrene resin (PS), acrylonitrile-butadiene-styrene terpolymer (ABS), styrene-acrylonitrile copolymer (SAN) and the like. In addition, the method can also be used in the industries of pharmacy, dye, pesticide, mineral separation and the like, and has wide application.
There are two main known processes for preparing styrene: (1) preparing styrene by directly carrying out thermal dehydrogenation on ethylbenzene in a catalytic manner; (2) one patent describing a process for the combined preparation of styrene and propylene oxide, commonly referred to as the POSM process, is U.S. Pat. No.3,3351635, which, in general, comprises the following steps: (a) benzene and ethylene are subjected to alkylation reaction to produce ethylbenzene; (b) reacting ethylbenzene with oxygen or air to form ethylbenzene hydroperoxide; (c) under the condition of an epoxidation Ti-Si molecular sieve catalyst, ethylbenzene hydroperoxide reacts with propylene to generate propylene oxide and 1-phenethyl alcohol (also called alpha-phenyl ethanol); (d) the resulting 1-phenylethyl alcohol is dehydrated to styrene in the presence of a suitable dehydration catalyst.
There are two main processes known in the art for the dehydration of 1-phenylethyl alcohol to produce styrene, gas phase dehydration and liquid phase dehydration, respectively.
Solid acid catalysts such as alumina or titania are commonly used in gas phase dehydration processes, as described in US3442963 and US 3658928. The liquid phase process is preferred from an economic standpoint because the gas phase process requires frequent regeneration to remove carbon deposits from the catalyst surface to ensure acceptable conversion and selectivity.
In the liquid phase dehydration method, a homogeneous acid such as sulfuric acid, phosphoric acid and a p-toluenesulfonic acid catalyst is usually used independently, see US patent No. 3526674, and in the liquid phase method, in order to ensure a high conversion rate, the catalyst and the 1-phenylethyl alcohol raw material need a certain retention time in a reactor, and the generated styrene cannot be separated from the reaction system in time and stays in the reactor under high temperature and liquid phase strong acidic conditions, so that the generated styrene is polymerized and converted into byproducts such as recombinant components, and the yield of the styrene is reduced. Even with conventional reactive distillation processes, up to 5% styrene polymer is still formed.
Meanwhile, the acidic catalyst with large molecular weight is easy to polymerize with styrene, so that the dosage of the catalyst is large, and the side reaction of generating heavy components is aggravated. In addition, the traditional kettle type reactor has large volume and high reaction temperature, which causes severe corrosion of the reactor.
In order to solve the problems, one of the existing methods for synthesizing styrene is to use 1-phenethyl alcohol to carry out reaction, rectification and dehydration under the conditions of high temperature and reduced pressure, but the reaction and separation are carried out in the same equipment, the dehydration effect is poor, the reaction retention time is long, reaction products and catalysts cannot be separated from heavy components in time, the styrene and the heavy components are further polymerized, and the reduction of the overall yield caused by the polymerization of the styrene cannot be fundamentally avoided.
Meanwhile, the liquid phase dehydration adopts a catalyst of a p-toluenesulfonic acid macromolecule, a large amount of catalyst needs to be added in the traditional reactor to ensure higher 1-phenylethylene alcohol conversion rate, and the catalyst can participate in styrene polymerization to cause double losses of the catalyst and the styrene.
In conclusion, it is necessary to develop a new catalyst and a new reaction process for preparing styrene by dehydrating 1-phenylethyl alcohol, so that the amount of the catalyst can be reduced, the generation of byproducts can be reduced, and the yield of styrene products can be improved.
Disclosure of Invention
In the present invention, a novel process for preparing styrene from 1-phenylethyl alcohol has been found, and a more preferable complex catalyst suitable for the system has been found, which not only can increase the conversion rate of 1-phenylethyl alcohol, but also can reduce the generation of by-products such as styrene polymers, greatly increase the yield of styrene and reduce the amount of catalyst used.
In order to realize one aspect of the above purpose, the invention adopts the following technical scheme:
the compound catalyst for preparing styrene is a compound catalyst formed by compounding a sulfonic acid catalyst and an inhibitor.
In one embodiment, the sulfonic acid catalyst is methanesulfonic acid and the inhibitor is one or both of p-methoxyphenol and p-phenolformic acid; preferably, the compounding weight ratio of the sulfonic acid catalyst to the inhibitor is 1: 10-10: 1, such as 1: 5-5: 1, and more preferably 1: 2-2: 1.
In order to achieve another aspect of the above object, the present invention adopts the following technical solutions:
a process for preparing styrene, the process comprising:
(a) sending a mixture of the compound catalyst, 1-phenethyl alcohol and heavy components of a circulating reaction medium into a dehydration reactor for dehydration reaction to obtain a dehydrated product stream;
(b) flashing the dehydrated product stream in the step (a) through a flash tank to separate out the heavy component and the inhibitor of the circulating reaction medium, discharging the separated heavy component and the separated inhibitor of the circulating reaction medium as a liquid-phase product from the bottom of the flash tank and recycling at least part of the liquid-phase product, and obtaining a gas-phase product containing styrene from the top of the flash tank;
(c) sending the gas-phase product flashed out in the step (b) to a downstream dehydration separation tower for further rectification separation so as to obtain a styrene product stream at the top of the tower, and recycling at least part of the bottom product.
In the present invention, the heavy component of the circulating reaction medium may also be referred to as a heavy component, a circulating heavy component, or the like for short, and is a liquid phase having a boiling point of 210 ℃ or higher, and mainly contains styrene dimer, trimer, or the like.
In one embodiment, in step (a) of the present invention, a mixture of 1-phenylethyl alcohol, a complex catalyst and heavy components in a circulating reaction medium is fed into a dehydration reactor to carry out a rapid dehydration reaction; the dehydration reactor may be a shell and tube reactor.
In one embodiment, in the step (a), before the 1-phenylethyl alcohol and the heavy component of the circulating reaction medium enter the dehydration reactor, a static mixer is needed to fully mix the 1-phenylethyl alcohol and the heavy component solvent of the circulating reaction medium; wherein, the compound catalyst can be premixed with the 1-phenethyl alcohol or directly added from the top of the dehydration separation tower. Optionally, the sulfonic acid catalyst can also be directly added from the top of the dehydration separation tower to supplement the consumption of the sulfonic acid catalyst, so that the compounding weight ratio of the sulfonic acid catalyst to the inhibitor is 1: 10-10: 1, such as 1: 5-5: 1, and more preferably 1: 2-2: 1.
In one embodiment, the compound catalyst is a dehydration catalyst and an inhibitor which are mixed for compound use. The dehydration catalyst is a catalyst (or called as dehydration catalyst) for catalyzing dehydration reaction, preferably a sulfonic acid catalyst; the inhibitor is an inhibitor for inhibiting side reactions (or called side reaction inhibitor, or simply inhibitor). Preferably, the sulfonic acid catalyst with the boiling point lower than 180 ℃ is compounded with the inhibitor with the boiling point higher than 210 ℃, more preferably one or two of methane sulfonic acid, p-methoxyphenol and p-phenol formic acid, and more preferably the methane sulfonic acid and the p-phenol formic acid. The compounding ratio of the sulfonic acid catalyst to the inhibitor is preferably 1: 10-10: 1, more preferably 1: 5-5: 1, and more preferably 1: 2-2: 1.
Typically, the complexed catalyst in the mixture of step (a) comprises a freshly added catalyst and the 1-phenylethyl alcohol in the mixture of step (a) comprises a freshly added 1-phenylethyl alcohol feedstock.
In one embodiment, the amount of freshly added reconstituted catalyst added is at least 20ppm (i.e., the amount of freshly added reconstituted catalyst added is at least twenty parts per million by weight of the freshly added 1-phenylethyl alcohol feedstock), preferably in the range of 30 to 200ppm, more preferably 50 to 100ppm, based on the weight of the freshly added 1-phenylethyl alcohol feedstock. The amount of complexed catalyst in the dehydration reactor is at least about 20ppm based on the weight of the 1-phenylethyl alcohol feedstock in the dehydration reactor when the dehydration reaction is occurring in the dehydration reactor (i.e., the amount of complexed catalyst in the dehydration reactor is at least twenty parts per million based on the weight of the 1-phenylethyl alcohol feedstock), preferably in the range of about 30 to 200ppm, more preferably about 50 to 100 ppm.
In one embodiment, in the step (a), in order to ensure a higher conversion rate, the feeding amount of the recycled reaction medium heavy component and the 1-phenylethyl alcohol in the feed of the dehydration reactor needs to ensure a proper ratio, and the weight ratio (also called the recycle ratio) of the recycled reaction medium heavy component to the freshly added 1-phenylethyl alcohol raw material is preferably 5:1 to 40:1, more preferably 5:1 to 30:1, and still more preferably 10:1 to 20: 1. Wherein the heavy component of the circulating reaction medium in the feed of the dehydration reactor can comprise the heavy component of the circulating reaction medium from the bottom of the flash tank and/or the heavy component of the circulating reaction medium from the bottom of the dehydration separation tower.
In one embodiment, the temperature of the dehydration reactor in the step (a) is preferably 100 ℃ to 250 ℃, more preferably 160 ℃ to 210 ℃, more preferably 180 ℃ to 200 ℃, and preferably, the reaction temperature should be lower than the boiling point of the liquid phase reaction medium; the pressure of the dehydration reactor in the step (a) is the same as that of the flash tank, and is 30-70 kPa, preferably 40-60 kPa. The residence time in the dehydration reactor is 30 to 90 seconds.
In one embodiment, in step (b) of the present invention, the dehydrated product stream generated by the reaction comprises water, styrene, unreacted 1-phenylethyl alcohol, the sulfonic acid catalyst, the inhibitor and heavy components of the circulating reaction medium, and the like, and is subjected to flash separation by a flash tank, wherein the liquid phase at the bottom of the flash tank mainly comprises the heavy components of the circulating reaction medium and the inhibitor, and the heavy components of the circulating reaction medium cannot further undergo polymerization reaction with styrene in the presence of the inhibitor. Mixing at least partial liquid phase (for example, at least 98% of liquid phase) at the bottom of the flash tank with the 1-phenethyl alcohol raw material and all heavy components recycled from the bottom of the dehydration separation tower, and then sending the obtained mixture into the dehydration reactor for dehydration reaction again to realize the circulation of the heavy component of the circulating reaction medium and the compound catalyst; and discharging the other part of the liquid phase except at least part of the liquid phase at the bottom of the flash tank, so as to discharge redundant heavy components of the circulating reaction medium and further perform waste liquid treatment. Wherein the gas phase at the top of the flash tank mainly comprises water, styrene, a small amount of 1-phenylethyl alcohol and a sulfonic acid catalyst.
In one embodiment, in step (b), the pressure in the flash tank is controlled so that the heavies and inhibitors of the liquid phase recycle reaction medium exiting the dehydration reactor are not carried out of the flash tank, while maintaining a substantial portion of the unreacted 1-phenylethyl alcohol at the bottom of the flash tank and recycled to the reactor inlet. The pressure of the flash tank is preferably 30 to 70kPa, more preferably 40 to 60 kPa.
In one embodiment, in step (c) of the present invention, the gas phase mainly containing styrene, 1-phenylethyl alcohol, sulfonic acid catalyst, etc. flashed in step (b) is sent to a downstream dehydration separation tower for further separation, styrene and water are extracted from the top of the separation tower, and a styrene product stream is obtained after the separation of an aqueous phase after condensation at the top of the separation tower, wherein the separated aqueous phase part reflows at the top of the separation tower to recover the sulfonic acid catalyst; at least part (preferably all) of the sulfonic acid catalyst recovered from the bottom of the dehydration separation tower, the unreacted 1-phenethyl alcohol, a small amount of flash evaporated circulating reaction medium heavy components, the inhibitor and the like are sent to a dehydration reactor for further dehydration reaction, thereby forming the recovery circulation of the complex catalyst and the 1-phenethyl alcohol.
In one embodiment, in the step (c), the pressure of the top of the dehydration separation column is in a range of 0 to 40kPa, preferably 5 to 30kPa, more preferably 5 to 25kPa, and still more preferably 10 to 20 kPa.
In one embodiment, in step (c), the aqueous phase separated at the top of the dehydration separation column is refluxed to recover the sulfonic acid catalyst in styrene while controlling the temperature at the top of the column. The compound catalyst can be added together with the reflux water phase from the top of the dehydration separation tower. The temperature of the top of the tower is controlled to be 80-110 ℃, and preferably 80-90 ℃.
In one embodiment of the present invention, the method further comprises step (d): removing acid components from a styrene product stream mainly containing styrene and water obtained from the top of the dehydration separation tower through alkaline resin adsorption to obtain crude styrene; wherein, the acid component comprises sulfonic acid catalyst, the resin can be weak base anion exchange resin, such as D301 alkaline resin, the resin dosage ensures that the space velocity of the whole liquid phase can be 0.2 BV-1 BV, such as 0.5 BV.
In one embodiment, in order to further reduce styrene polymerization, a dehydration polymerization inhibitor can be injected, and the dehydration polymerization inhibitor can be injected at multiple points, including a flash tank gas phase discharge pipeline, the top of a dehydration separation tower, crude styrene after resin deacidification, and the like.
In one embodiment, the dehydration polymerization inhibitor may be one of hydroquinone, p-tert-butyl catechol, di-tert-butyl p-cresol benzoquinone or a combination thereof, and is used in an amount of ten to fifty parts per million based on the weight of styrene.
In the present invention, the pressures are all absolute pressures.
Compared with the prior art, the invention has the following beneficial effects.
(1) The 1-phenethyl alcohol is dehydrated by adopting an external circulation reaction and rectification mode, and the conversion rate of the 1-phenethyl alcohol can reach more than 98 percent under the action of a compound catalyst.
(2) The complex catalyst is compounded by adopting one or two inhibitors of methane sulfonic acid, p-methoxyphenol and p-phenol formic acid, the dehydration catalyst and the side reaction inhibitor are separately circulated technically, the side reaction inhibitor always exists in heavy components, and the occurrence of side reactions is reduced.
(3) The residence time of reactants and products in the dehydration reactor is short, the product styrene is flashed off immediately after reaction, and the residence time of the styrene in a high-temperature environment is greatly reduced, so that heavy components generated by polymerization are reduced, and the selectivity can reach more than 98%.
(4) The catalyst consumption is less, the reaction temperature is lower under the condition of the same conversion rate, the reactor volume is small, and the corrosion risk of the reactor can be greatly reduced.
(5) By separately controlling the pressures of the reaction system and the separation system, the reaction conversion rate and the separation efficiency can be regulated and controlled, so that the operation flexibility of the device is increased.
Drawings
FIG. 1 is a schematic representation of one embodiment of the styrene production process of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail by the following embodiments in conjunction with the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one embodiment, as shown in FIG. 1, a 1-phenylethyl alcohol stream 1 and a liquid phase stream 5 containing heavy components of a circulating reaction medium are conveyed to a static mixer S-1 to be mixed to obtain a mixed stream 2, and a complex catalyst is mixed with the 1-phenylethyl alcohol stream 1 in advance or is injected from the top 9 of a dehydration separation tower C-1.
And (2) feeding the mixed material flow 2 mixed in the static mixer S-1 into a dehydration reactor R-1, and performing rapid dehydration reaction at the temperature of 100-250 ℃ and under the pressure of 30-70 kPa (same as the pressure of a flash tank) to obtain a dehydrated product flow 3 after reaction, wherein the weight ratio of the heavy component of the circulating reaction medium to the feeding amount of the freshly added 1-phenethyl alcohol is 5: 1-40: 1.
And (3) feeding the dehydrated product flow after reaction into a flash tank D-1, after flash separation, enabling gas phase material flows 4 such as styrene, water and part of unreacted 1-phenethyl alcohol to leave from the top of the flash tank and enter into a dehydration separation tower C-1, enabling at least part of liquid phase at the bottom of the flash tank to be used as liquid phase material flow 5 containing heavy components of a circulating reaction medium to circulate back to the dehydration reactor R-1, mixing the liquid phase with the 1-phenethyl alcohol material flow 1 again in a static mixer S-1 before entering the dehydration reactor R-1, and discharging the other part of the liquid phase at the bottom of the flash tank through an effluent material flow 6.
The generated styrene is separated by a dehydration separation tower C-1, the styrene is extracted from the tower top 9 of the dehydration separation tower and is sent to an alkaline resin adsorption bed D-2 through a pipeline 7, the unreacted 1-phenethyl alcohol, the sulfonic acid catalyst, the inhibitor and the heavy component of the circulating reaction medium at the bottom of the dehydration separation tower are circulated back to a dehydration reactor R-1 along with a circulating material flow 8, the water phase is refluxed from the tower top of the dehydration separation tower C-1, the temperature is controlled to be 80-90 ℃, and the complex catalyst and the water phase are added together.
The styrene-containing material from line 7 is desorbed with the basic resin in the basic adsorbent bed D2, and the crude styrene obtained after adsorption is discharged through line 10.
The analysis method comprises the following steps:
the 1-phenylethyl alcohol conversion is the amount of 1-phenylethyl alcohol consumed as a percentage of the initial amount of 1-phenylethyl alcohol for conversion to Styrene (SM) and can be calculated from formula (1):
1-Phenylethanol conversion rate (1) SM molar flow at the top of the dehydration separation column/molar flow of 1-Phenylethanol fed to the dehydration reactor
The styrene selectivity is the percentage of 1-phenylethyl alcohol consumed by converting the styrene to the total consumption of 1-phenylethyl alcohol, and can be represented by the ratio of the SM molar flow at the top of the dehydration separation tower to the 1-phenylethyl alcohol consumed by the total reaction (the molar flow of 1-phenylethyl alcohol consumed by the total reaction can be obtained by subtracting the 1-phenylethyl alcohol molar flow discharged at the top of the dehydration separation tower from the 1-phenylethyl alcohol molar flow fed into the dehydration reactor), and can be calculated by the formula (2):
styrene selectivity (SM molar flow at the top of the dehydration and separation column/(1-phenethyl alcohol molar flow fed into the reactor-1-phenethyl alcohol molar flow discharged at the top of the dehydration and separation column) (2)
Examples 1 to 11
Controlling the pressure of a flash tank to be 50kPa, the top pressure of a separation tower to be 30kPa, the temperature of a dehydration reactor to be 200 ℃ and the pressure to be 50kPa, adding a complex catalyst of methane sulfonic acid and p-phenol formic acid according to a complex ratio n based on the weight of the freshly added 1-phenethyl alcohol raw material, wherein the circulation ratio (the mass ratio of the weight of the circulated circulating reaction medium to the feeding mass of the freshly added 1-phenethyl alcohol) is 10: 1-32: 1. The obtained styrene-containing material is deacidified by adopting D301 alkaline resin, and the airspeed of the resin adsorption bed is 0.5 BV. The results are shown in table 1 below.
TABLE 1
Examples 12 to 18
The circulation ratio is 15, the retention time is 60s, based on the weight of the freshly added 1-phenethyl alcohol raw material, the methane sulfonic acid and the P-phenol formic acid catalyst are compounded according to the ratio of 1 to 1, the addition amount of the compounded catalyst is 100ppm, and the pressure P of a flash tank 1 kPa, top pressure P of the separation column 2 kPa wherein the dehydration reactor pressure is the same as the flash tank pressure, is P 1 kPa. The obtained styrene-containing material is deacidified by adopting D301 alkaline resin, and the airspeed of the resin adsorption bed is 0.5 BV. The reaction results are shown in Table 2.
TABLE 2
The results show that the conversion rate of 1-phenethyl alcohol can reach more than 98 percent and the selectivity can reach more than 98.5 percent by controlling the temperature of the dehydration reactor R-1 and adjusting the circulation ratio.
Claims (11)
1. A process for the preparation of styrene, characterized in that it comprises:
(a) sending a mixture containing a complex catalyst, 1-phenethyl alcohol and heavy components of a circulating reaction medium into a dehydration reactor for dehydration reaction to obtain a dehydrated product stream;
(b) flashing the dehydrated product in the step (a) through a flash tank to separate out heavy components and an inhibitor of the circulating reaction medium, discharging the separated heavy components and the inhibitor as liquid phase products from the bottom of the flash tank, recycling at least part of the liquid phase products, and obtaining a gas phase product containing styrene from the top of the flash tank;
(c) sending the gas-phase product flashed out in the step (b) to a downstream dehydration separation tower for further rectification separation so as to obtain a styrene product stream at the top of the tower, and recycling at least part of the bottom product;
the complex catalyst is formed by compounding a sulfonic acid catalyst and an inhibitor, the sulfonic acid catalyst is methane sulfonic acid, and the inhibitor is one or two of p-methoxyphenol and p-phenol formic acid.
2. The method according to claim 1, wherein the weight ratio of the sulfonic acid catalyst to the inhibitor is 1: 10-10: 1.
3. The method of claim 2, wherein the sulfonic acid catalyst is methane sulfonic acid and the inhibitor is p-phenol formic acid.
4. The process according to any one of claims 1 to 3, wherein the reconstituted catalyst in the mixture in step (a) comprises a freshly added catalyst, the 1-phenylethyl alcohol in the mixture comprises a freshly added 1-phenylethyl alcohol feedstock, and the freshly added reconstituted catalyst is added in an amount of 30 to 200ppm based on the weight of the freshly added 1-phenylethyl alcohol feedstock.
5. The process according to claim 4, wherein in step (a) the weight ratio of the recycled reaction medium inventory to the freshly added 1-phenylethyl alcohol feedstock in the feed to the dehydration reactor is from 5:1 to 40: 1.
6. The method according to claim 5, wherein the temperature of the dehydration reactor is 100 ℃ to 250 ℃ and the pressure is 30kPa to 70 kPa.
7. The process according to any one of claims 1 to 3, wherein the pressure of the flash tank in step (b) is 30 to 70 kPa.
8. The process according to any one of claims 1 to 3, wherein the pressure at the top of the dehydration separation column in the step (c) is 0 to 40kPa, and the temperature at the top of the column is 80 to 110 ℃.
9. The method according to claim 4, wherein the mixture in step (a) is obtained by: mixing the freshly added 1-phenethyl alcohol and the heavy component of the circulating reaction medium by an upstream static mixer before feeding the 1-phenethyl alcohol and the heavy component of the circulating reaction medium into the dehydration reactor; wherein the freshly added compound catalyst and the freshly added 1-phenylethyl alcohol are mixed in advance or are directly added from the top of the dehydration separation tower.
10. A process according to any one of claims 1 to 3, wherein in step (c) the overhead output of the dehydration separation column comprises styrene and water, and liquid phase water is separated after overhead condensation to give the styrene product stream, and the liquid phase water is partially refluxed overhead.
11. The method of claim 10, further comprising step (d):
and removing acid components from the styrene product stream through alkaline resin adsorption to obtain a styrene product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911201679.XA CN110776389B (en) | 2019-11-29 | 2019-11-29 | Compound catalyst and method for preparing styrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911201679.XA CN110776389B (en) | 2019-11-29 | 2019-11-29 | Compound catalyst and method for preparing styrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110776389A CN110776389A (en) | 2020-02-11 |
| CN110776389B true CN110776389B (en) | 2022-08-05 |
Family
ID=69393676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911201679.XA Active CN110776389B (en) | 2019-11-29 | 2019-11-29 | Compound catalyst and method for preparing styrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110776389B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0106323A1 (en) * | 1982-10-14 | 1984-04-25 | Kuraray Co., Ltd. | Process for producing isoprene |
| JPS6172727A (en) * | 1984-09-17 | 1986-04-14 | Nippon Sheet Glass Co Ltd | Production of styrene |
| US5639928A (en) * | 1993-03-11 | 1997-06-17 | Arco Chemical Technology, L.P. | Dehydration of 1-phenyl ethanol |
| CN1854116A (en) * | 2005-04-29 | 2006-11-01 | 北京金源化学集团有限公司 | Production of phenylethylene compound |
| CN102361838A (en) * | 2009-03-23 | 2012-02-22 | 莱昂德尔化学技术公司 | Dehydration of 1-phenyl ethanol |
| CN105152844A (en) * | 2015-08-17 | 2015-12-16 | 山东成泰化工有限公司 | Method for preparing isobutylene from tert-butyl alcohol |
| CN105175210A (en) * | 2015-09-08 | 2015-12-23 | 山东成泰化工有限公司 | Method for preparing isobutylene by tert butyl alcohol |
-
2019
- 2019-11-29 CN CN201911201679.XA patent/CN110776389B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0106323A1 (en) * | 1982-10-14 | 1984-04-25 | Kuraray Co., Ltd. | Process for producing isoprene |
| JPS6172727A (en) * | 1984-09-17 | 1986-04-14 | Nippon Sheet Glass Co Ltd | Production of styrene |
| US5639928A (en) * | 1993-03-11 | 1997-06-17 | Arco Chemical Technology, L.P. | Dehydration of 1-phenyl ethanol |
| CN1854116A (en) * | 2005-04-29 | 2006-11-01 | 北京金源化学集团有限公司 | Production of phenylethylene compound |
| CN102361838A (en) * | 2009-03-23 | 2012-02-22 | 莱昂德尔化学技术公司 | Dehydration of 1-phenyl ethanol |
| CN105152844A (en) * | 2015-08-17 | 2015-12-16 | 山东成泰化工有限公司 | Method for preparing isobutylene from tert-butyl alcohol |
| CN105175210A (en) * | 2015-09-08 | 2015-12-23 | 山东成泰化工有限公司 | Method for preparing isobutylene by tert butyl alcohol |
Non-Patent Citations (1)
| Title |
|---|
| 掺杂ZnS纳米颗粒的合成和表征;项伟荣;《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》;20140615(第06期);B020-418 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110776389A (en) | 2020-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4504135B2 (en) | Method for producing t-butanol | |
| CN101481307B (en) | Method for separating acetic acid and sec-butyl acetate from reaction products | |
| CN103086829B (en) | Butylene oxidation-dehydrogenation waste water recycling method | |
| US11299450B2 (en) | System and process for co-producing dimethyl carbonate and ethylene glycol | |
| CN110759801B (en) | Method for producing diisobutylene by mixing C4 | |
| CN106588589A (en) | Purification method for polyoxymethylene dimethyl ether(PODE) | |
| CN103964997B (en) | The treatment process of butylene oxidation-dehydrogenation product | |
| CN111825538B (en) | Method for continuously producing pseudo ionone | |
| KR100703914B1 (en) | Method for producing propylene hydroformylation products and acrylic acid and/or acrolein | |
| CN105980338B (en) | By the method for the raw material production 1,3-butadiene comprising ethyl alcohol | |
| US20030040637A1 (en) | Process for the epoxidation of olefins | |
| CN102452934B (en) | Preparation method of sec-butyl acetate | |
| EP1293505A1 (en) | Process for the epoxidation of olefins | |
| CN112250534B (en) | Method for reducing unit consumption of cumene in process of producing epoxypropane by cumene co-oxidation method | |
| CN108218678B (en) | Method and device for separating and refining polymethoxy dimethyl ether | |
| CN110776389B (en) | Compound catalyst and method for preparing styrene | |
| CN115536504B (en) | Partition wall catalytic reaction method and device for polymethoxy dimethyl ether synthesis | |
| CN111269096A (en) | Method for preparing ethylene glycol tert-butyl ether | |
| CN108358762B (en) | Five-stage separation method and device of polymethoxy dimethyl ether | |
| US4760203A (en) | Process for the production of isopropyl alcohol | |
| JPS60233024A (en) | Production of tert-butyl alcohol | |
| WO2013012203A2 (en) | Method of preparing cumyl alcohol and method of preparing phenol, acetone and alpha methyl styrene | |
| CN110372478B (en) | Continuous catalytic extraction method for preparing methylal | |
| US20220371978A1 (en) | Systems and methods for mtbe production | |
| CN113087602A (en) | Production and refining method of polymethoxy dimethyl ether |
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 |