CN112920026B - Preparation method and device of propylene glycol primary mono-tert-butyl ether - Google Patents
Preparation method and device of propylene glycol primary mono-tert-butyl ether Download PDFInfo
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- CN112920026B CN112920026B CN201911237108.1A CN201911237108A CN112920026B CN 112920026 B CN112920026 B CN 112920026B CN 201911237108 A CN201911237108 A CN 201911237108A CN 112920026 B CN112920026 B CN 112920026B
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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
- C07C41/05—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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- 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
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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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
- C07C41/34—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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Abstract
The invention relates to a preparation method and a device of propylene glycol primary mono-tertiary butyl ether, the method comprises the steps of fully mixing raw materials with propylene glycol, sending the mixture into a reactor for etherification reaction, sending the mixture obtained by the reaction into a light component removal tower for removing unreacted mixed carbon four, sending a tower bottom extract into a dealcoholization tower for treatment, sending the tower top extract into a product refining tower for refining, obtaining propylene glycol primary mono-tertiary butyl ether product at the tower bottom of the product refining tower, sending the tower bottom extract of the dealcoholization tower into an alcohol refining tower, obtaining propylene glycol at the tower bottom of the alcohol refining tower, and recycling the propylene glycol back into the etherification reactor for reaction. The preparation and separation method for preparing the propylene glycol primary mono-tertiary butyl ether provided by the invention has the advantages that the propylene glycol primary mono-tertiary butyl ether has high selectivity of more than 95%, and the selectivity of the propylene glycol primary mono-tertiary butyl ether is more than 90%. The method has mild reaction conditions, safe and environment-friendly process, and the purity of the propylene glycol primary mono-tertiary butyl ether product reaches more than 99.9% through separation.
Description
Technical Field
The invention relates to a preparation method and a device of propylene glycol primary mono-tertiary butyl ether.
Background
After the ethanol gasoline for vehicles is popularized and used nationwide in 2020, MTBE is disabled. At present, domestic isobutene is mainly used for producing MTBE, and with popularization and use of ethanol gasoline for vehicles, a large amount of isobutene faces no available embarrassment. At the same time, the mixed C4 containing isobutene is not suitable for raw materials for other many purposes, such as sec-butyl acetate, butanone, alkylation oil and the like. Finding a new way to utilize isobutene is a problem to be solved urgently.
The propylene glycol butyl ether series is a very promising environment-friendly solvent because of its slightly toxic and more pleasant smell. The use of the detergent composition in industrial/household cleaning formulations is extremely safe and is accepted by many developed countries, especially japan. The evaporation rate is similar to that of ethylene glycol butyl ether, and the ethylene glycol butyl ether is a good substitute for the ethylene glycol butyl ether. The paint has wide application in the aspects of paint, cleaning agent, printing ink, leather and the like. In the process of dye dissolution, the dye can be used for replacing an alcoholic solvent, and is a good coupling agent. In addition, the propylene glycol butyl ether series can be used as a film forming additive for water-based paint, photoresist, PS plate cleaning, printing, electronic chemicals, jet engine fuel additives (waterproofing agents), extractants, high boiling point solvents and the like.
At present, the patent technology for synthesizing propylene glycol tertiary butyl ether is less, most of the prior art is used for synthesizing other propylene glycol ether substances, and the main method is that propylene oxide is subjected to ring opening and reaction with lower alcohols (such as methanol, ethanol, propanol, butanol and the like). The method has the advantages of complex product types, not only propylene glycol ethers, but also dipropylene glycol ethers and tripropylene glycol ethers, high reaction control difficulty, poor safety, poor reaction selectivity and low product purity.
Chinese patent CN201410448311.4 discloses a process for preparing glycol mono-tert-butyl ether by alkylation of glycol, liquefied petroleum gas and acid catalyst at 40-100 deg.c and 0.5-5.0MPa to obtain glycol mono-tert-butyl ether. The invention has the beneficial effects that: the liquefied petroleum gas containing isobutene can be used as a reaction raw material, dihydric alcohol and an acidic catalyst are matched, and the contact time and the reaction temperature of the reaction materials are controlled, so that a dihydric alcohol tertiary butyl ether crude product with high selectivity can be obtained.
Chinese patent CN201510434672.8 discloses a process for producing diol tert-butyl ether. The invention uses saturated dihydric alcohol and liquefied petroleum gas as raw materials, and is matched with certain reaction temperature, pressure and space velocity and uses a specific tubular reactor to carry out addition reaction, the saturated dihydric alcohol has high conversion rate, high reaction selectivity, no side reaction, environmental protection, wide applicability and high yield.
Chinese patent CN201410481274.7 discloses a method for synthesizing propylene glycol butyl ether, which is characterized in that: the butanol and propylene oxide are added into a high-pressure reaction kettle together with catalyst perchlorate with the dosage of 0.005-0.05% (w) according to the mol ratio of 1-5:1, the mixture is heated to 100-150 ℃ under the stirring condition and the reaction pressure is 0.2-0.5MPa, the mixture is reacted for 1-2 hours, the mixture of butanol, propylene glycol butyl ether and dipropylene glycol butyl ether is obtained, and the mixture is subjected to continuous rectification separation, so that the propylene glycol butyl ether product and the byproduct dipropylene glycol butyl ether are obtained. The perchlorate catalyst adopted by the invention has higher catalytic activity, low catalyst consumption and short reaction time, and meanwhile, the selectivity of the primary ether in the product is higher, and the monoether conversion rate is high, so that the method is suitable for industrial production.
The above patents are all methods for preparing glycol butyl ether, most of which are reaction parts, and do not relate to a separation method, but only patent CN201410481274.7 mentions that separation is carried out by adopting continuous rectification separation and by-products after reaction, but also does not relate to a specific separation method.
Other related patent technologies disclosed in the prior art are all related patents for preparing high-purity isobutene by using propylene glycol tertiary butyl ether and no propylene glycol mono tertiary butyl ether.
Patent CN107778123a discloses a method for preparing isobutene, which is to prepare high-purity isobutene in a circulating fluidized bed by using glycol ether generated by the reaction of C4 and glycol under the action of a molecular sieve catalyst.
CN204589030U, CN105985215A discloses a cracking system for preparing high purity isobutylene using propylene glycol tert-butyl ether. Compared with the MTBE cracking method, the method has the advantages of low cracking temperature, no need of water washing, low energy consumption, less tower, low investment and low running cost.
How to find a method for preparing propylene glycol primary mono-tertiary butyl ether with high conversion rate and high selectivity by utilizing the existing isobutene resources, and can effectively separate a reaction mixture to obtain the propylene glycol primary mono-tertiary butyl ether with high purity after separation, thus the method is a problem to be solved by the invention.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a method and a device for preparing propylene glycol primary mono-tertiary butyl ether with high conversion rate and high selectivity, can effectively separate a reaction mixture, and obtain the propylene glycol primary mono-tertiary butyl ether with high purity after separation.
The method provided by the invention comprises the following steps: (1) Fully mixing the raw materials with the carbon four and propylene glycol, and then sending the mixture into a reactor to carry out etherification reaction under the etherification reaction condition; (2) Sending the mixture obtained by the reaction into a light component removal tower, obtaining unreacted mixed carbon four at the top of the tower, and obtaining a mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol at the bottom of the tower; (3) Sending the mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol obtained at the bottom of the light component removing tower into a dealcoholization tower, obtaining the mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tertiary butyl ether at the bottom of the dealcoholization tower, and obtaining the mixture of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol at the top of the dealcoholization tower; (4) Sending the mixture of the propylene glycol primary mono-tertiary butyl ether, the C8 and the tertiary butanol obtained from the top of the dealcoholization tower into a product refining tower, obtaining the mixture of the tertiary butanol and the C8 from the top of the tower, and obtaining the propylene glycol primary mono-tertiary butyl ether product from the bottom of the tower; (5) And (3) sending the mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained at the bottom of the dealcoholization tower into an alcohol refining tower, obtaining the mixture of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether at the top of the alcohol refining tower, and obtaining propylene glycol at the bottom of the alcohol refining tower.
In the invention, under the selected technological conditions, propylene glycol and mixed carbon four are fully mixed by a mixer and then enter a reactor to react under the action of an etherification catalyst, and the reacted materials enter a separation system to refine the product.
The reaction equation is as follows:
during the synthesis of propylene glycol ethers, the following side reactions also occur in minor amounts:
in the present invention, the reactor is preferably a fixed bed reactor, and the catalyst is a macroporous strongly acidic cation exchange resin, which can be commercially available products. In the invention, the composition of the mixed C-IV is 30-40wt% of isobutane, 10-20wt% of n-butene, 10-20wt% of n-butane, 10-20wt% of isobutene, 10-20wt% of fumaric acid, 5-15wt% of n-butene, 0.01-0.1wt% of C-III and 0.1-0.5wt% of butadiene.
In the present invention, the reaction is controlled under reaction conditions such as a proper reaction temperature, a proper residence time, a proper alcohol-to-olefin ratio, a proper reaction pressure, etc., in order to control the conversion rate and the selectivity of the reaction. In the invention, the etherification reaction conditions are as follows: the reaction temperature is 40 to 80 ℃, preferably 45 to 75 ℃, more preferably 50 to 70 ℃, more preferably 55 to 70 ℃, still more preferably 60 to 70 ℃. Too high a reaction temperature results in more side reactions, more propylene glycol di-t-butyl ether is easily produced, and too low a reaction temperature results in too low an isobutene conversion in the mixed carbon four of the reaction raw materials.
In the present invention, the residence time of the etherification reaction is 100 to 150 minutes, preferably 105 to 145 minutes, more preferably 110 to 140 minutes, more preferably 115 to 135 minutes, more preferably 115 to 130 minutes, and further preferably 115 to 125 minutes. Too short residence time of the reaction results in too low conversion of isobutene in the mixed carbon four of the reaction raw materials, too long reaction time and easy generation of more byproducts.
In the present invention, the alcohol-to-olefin ratio means a molar ratio of propylene glycol to isobutylene in the mixed carbon four. In the present invention, the alcohol-to-olefin ratio is 2 to 5:1, preferably 2.2 to 4.8:1, more preferably 2.4 to 4.6:1, more preferably 2.5 to 4.5:1, more preferably 2.8 to 4.2:1, more preferably 3 to 4:1, and further preferably 3.2 to 3.8:1; the reaction pressure is 0.5 to 1.5MPa, preferably 0.6 to 1.4MPa, more preferably 0.7 to 1.3MPa, still more preferably 0.8 to 1.2MPa, and still more preferably 0.9 to 1.1MPa.
In the invention, in the mixture after reaction, 20-50wt% of propylene glycol, 30-70wt% of mixed carbon four, 10-25wt% of propylene glycol primary mono-tertiary butyl ether, 0.5-3wt% of propylene glycol Zhong Shanshu butyl ether, 0.1-2wt% of propylene glycol di-tertiary butyl ether, 0.01-1wt% of C8 and 0.01-1wt% of tertiary butanol.
In the invention, the tower top pressure of the light component removing tower is 0.3-0.6MPa, preferably 0.35-0.55MPa, more preferably 0.35-0.5MPa, and even more preferably 0.35-0.45MPa; the overhead temperature is in the range of from 35 to 70 ℃, preferably 40 to 65 ℃, more preferably 40 to 60 ℃, more preferably 40 to 55 ℃, still more preferably 45 to 50 ℃, and the reflux ratio is in the range of from 1 to 5:1, preferably 1.5 to 4.5:1, more preferably 2 to 4:1, more preferably 2 to 3.5:1, still more preferably 2 to 3:1.
In the invention, the boiling point of propylene glycol is 188 ℃, the boiling point of tert-butyl alcohol is 82.47 ℃, the boiling point of C8 (trimethylpentene) is 101.53 ℃, the boiling point of propylene glycol primary mono-tert-butyl ether is 152 ℃, the boiling point of propylene glycol Zhong Shanshu butyl ether is 162 ℃, and the boiling point of propylene glycol di-tert-butyl ether is 170 ℃. Wherein, the tert-butyl alcohol and C8 can form an azeotrope, the boiling point of the azeotrope is 78.03 ℃, and the composition of the azeotrope is 54.03 percent of tert-butyl alcohol and C845.97 percent.
In the present invention, the theoretical plate number of the dealcoholization tower is 40 to 80, preferably 42 to 75, more preferably 45 to 70, still more preferably 48 to 65, still more preferably 50 to 60; the feed inlet is arranged at 18-38 theoretical plates, preferably 20-35 theoretical plates, more preferably 22-30 theoretical plates, and even more preferably 22-28 theoretical plates; the pressure at the top of the tower is normal pressure, the temperature at the top of the tower is 140-150 ℃, preferably 141-150 ℃, more preferably 142-150 ℃, more preferably 143-149 ℃, and even more preferably 144-148 ℃; the bottom temperature is 185-195 ℃, preferably 186-194 ℃, more preferably 187-193 ℃, more preferably 187-192 ℃, further preferably 188-191 ℃, and the reflux ratio is 1-5:1, preferably 1.5-4.5:1, more preferably 2-4:1, more preferably 2-3.5:1, further preferably 2-3:1.
In the present invention, the theoretical plate number of the product purifying column is 20 to 60, preferably 25 to 55, more preferably 25 to 50, more preferably 28 to 45, more preferably 30 to 40, still more preferably 30 to 35; the feed inlet is arranged at 11-32 theoretical plates, preferably 13-28 theoretical plates, more preferably 14-26 theoretical plates, more preferably 16-21 theoretical plates, and further preferably 16-18 theoretical plates; the pressure at the top of the tower is normal pressure, the temperature at the top of the tower is 100-120 ℃, preferably 102-118 ℃, more preferably 104-116 ℃, more preferably 105-115 ℃, more preferably 106-114 ℃, and further preferably 108-112 ℃; the bottom temperature is 150-170 ℃, preferably 151-168 ℃, more preferably 152-166 ℃, more preferably 153-165 ℃, more preferably 154-164 ℃, more preferably 155-162 ℃, more preferably 156-160 ℃ and more preferably 157-158 ℃; the reflux ratio is 20-50:1, preferably 22-48:1, more preferably 25-45:1, more preferably 28-42:1, more preferably 30-40:1, more preferably 32-40:1, more preferably 35-40:1, and even more preferably 38-40:1. In the present invention, C8 and tertiary butanol may be separated from propylene glycol primary mono-tertiary butyl ether by utilizing the property that tertiary butanol and C8 are capable of forming an azeotrope.
In the present invention, the theoretical plate number of the alcohol refining column is 30 to 60, preferably 32 to 58, more preferably 35 to 55, more preferably 35 to 52, more preferably 35 to 50, more preferably 35 to 48, more preferably 35 to 45, and even more preferably 38 to 42; the feed inlet is arranged in 20-40 blocks, preferably 22-38 blocks, more preferably 25-35 blocks, more preferably 25-32 blocks, more preferably 25-30 blocks, and further preferably 25-28 blocks; the temperature of the tower top is 140-160 ℃, preferably 142-158 ℃, more preferably 142-155 ℃, more preferably 142-152 ℃, more preferably 142-150 ℃, and more preferably 145-150 ℃; the bottom temperature is 180-200 ℃, preferably 182-198 ℃, more preferably 185-195 ℃, more preferably 187-195 ℃, more preferably 188-195 ℃, more preferably 189-195 ℃, more preferably 190-194 ℃ and the reflux ratio is 10-20:1, preferably 11-19:1, more preferably 12-18:1, more preferably 13-17:1, and even more preferably 14-16:1.
In the invention, propylene glycol obtained at the bottom of the alcohol refining tower is recycled to the etherification reactor for reaction.
In the invention, the mixture of C8 and tertiary butanol obtained from the top of the product refining tower enters a product intermediate tank as a byproduct, and can be directly sold.
In the invention, the mixture of the propylene glycol Zhong Shanshu butyl ether and the propylene glycol di-tert-butyl ether obtained from the top of the alcohol refining tower can also be taken as a byproduct to enter a product intermediate tank for direct sales.
According to another aspect of the invention, there is provided a propylene glycol primary mono-tertiary butyl ether preparation device, which is characterized by comprising an etherification reactor, a light component removal tower, a dealcoholization tower, a product refining tower and an alcohol refining tower which are sequentially connected, wherein each of the light component removal tower, the dealcoholization tower, the product refining tower and the alcohol refining tower comprises a tower top condenser, a reflux tank, a tower bottom reboiler, a feed port, a tower top discharge port and a tower bottom discharge port, the etherification reactor is provided with the feed port and the discharge port, the etherification reactor discharge port is connected with the light component removal tower feed port through a pipeline, the dealcoholization tower bottom discharge port is connected with the dealcoholization tower feed port through a pipeline, the dealcoholization tower bottom discharge port is connected with the product refining tower feed port through a pipeline, and the dealcoholization tower bottom discharge port is connected with the alcohol refining tower feed port through a pipeline.
Preferably, the bottom discharge port of the alcohol refining tower is connected with the feed port of the etherification reactor through a pipeline.
Further, a top discharge hole of the product refining tower is connected with a mixture product intermediate tank of C8 and tertiary butanol.
Further, the top outlet of the alcohol refining tower is connected with a mixture product intermediate tank of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether.
THE ADVANTAGES OF THE PRESENT INVENTION
The invention provides a preparation and separation method and a device for preparing propylene glycol primary mono-tertiary butyl ether, wherein the propylene glycol primary mono-tertiary butyl ether has high selectivity of more than 95 percent, and the propylene glycol primary mono-tertiary butyl ether has selectivity of more than 90 percent. The method has mild reaction conditions, safe and environment-friendly process, and the purity of the propylene glycol primary mono-tertiary butyl ether product reaches more than 99.9% through separation.
Drawings
FIG. 1 is a flow chart of a process for preparing primary mono-tertiary butyl ether of propylene glycol in accordance with the present invention.
Wherein 1 is a mixed carbon four feed, 2 is propylene glycol, 3 is a reactor, 4 is a mixture after reaction, 5 is a light component removal column, 6 is a mixed carbon four, 7 is a mixture of a light component removal column top condenser, 8 is a light component removal column top reflux drum, 9 is a light component removal column top reflux, 10 is a light component removal column top extraction, 11 is a light component removal column bottom reboiler, 12 is a light component removal column bottom extraction material, 13 is a dealcoholization column, 14 is a dealcoholization column top extraction material, 15 is a dealcoholization column top condenser, 16 is a dealcoholization column top reflux drum, 17 is a dealcoholization column top reflux, 18 is a mixture of propylene glycol primary mono-tert-butyl ether, tert-butanol and C8, 19 is a dealcoholization column bottom reboiler, 20 is a dealcoholization column bottom extraction material, 21 is a product refining column, 22 is a product refining column overhead product, 23 is a product refining column overhead condenser, 24 is a product refining column overhead reflux drum, 25 is a product refining column overhead reflux, 26 is a mixture of tertiary butanol and C8, 27 is a product refining column bottom reboiler, 28 is a product propylene glycol primary mono-tertiary butyl ether, 29 is an alcohol refining column, 30 is an alcohol refining column overhead product, 31 is an alcohol refining column overhead condenser, 32 is an alcohol refining column overhead reflux drum, 33 is an alcohol refining column overhead reflux drum, 34 is a mixture of by-product propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tertiary butyl ether, 35 is an alcohol refining column bottom reboiler, and 36 is an alcohol refining column bottom product propylene glycol.
Detailed Description
The invention is further illustrated by the following examples. However, the present invention is not limited to the following examples, and various changes may be made to the present invention within the scope of the gist of the present invention, and these changes are still included in the scope of the present invention.
As shown in figure 1, the preparation device of propylene glycol primary mono-tertiary butyl ether is characterized by comprising an etherification reactor 3, a light component removing tower 5, a dealcoholization tower 13, a product refining tower 21 and an alcohol refining tower 29 which are sequentially connected, wherein the light component removing tower 5, the dealcoholization tower 13, the product refining tower 21 and the alcohol refining tower 29 respectively comprise a tower top condenser (7,15,23,31), a reflux tank (8,16,24,32), a tower bottom reboiler (11,19,27,35), a feed port, a tower top discharge port and a tower bottom discharge port, the etherification reactor 3 is provided with a feed port and a discharge port, the discharge port of the etherification reactor 3 is connected with the feed port of the light component removing tower 5 through a pipeline, the discharge port of the tower bottom of the light component removing tower 5 is connected with the feed port of the dealcoholization tower 13 through a pipeline, the discharge port of the tower top of the dealcoholization tower 13 is connected with a tower top reflux tank 16 through a pipeline, the discharge port of the tower top reflux tank 16 is connected with the feed port of the product refining tower 21, and the bottom discharge port of the dealcoholization tower 13 is connected with the feed port of the alcohol refining tower 29 through a pipeline.
The bottom discharge port of the alcohol refining tower 29 is connected with the feed port of the etherification reactor 3 through a pipeline.
The top outlet of the product refining tower 21 is connected with a mixture product intermediate tank of C8 and tertiary butanol.
The outlet of the top of the alcohol refining tower 29 is connected with a mixture product intermediate tank of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether.
The preparation method of the propylene glycol primary mono-tertiary butyl ether comprises the following steps:
(1) Fully mixing raw materials with carbon number four 1 and propylene glycol 2, and then sending the mixture into a reactor 3, and carrying out etherification reaction under the etherification reaction condition; (2) The reacted mixture 4 is sent to a light component removal tower 5, unreacted mixed carbon four 6 is obtained at the tower top, part of the mixture is taken as a tower top reflux 9 of a dehydrogenation component after passing through a tower top reflux tank 8 of the light component removal tower, part of the mixture is taken as a tower top reflux 10 of the dehydrogenation component, and the mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol is obtained at the tower bottom (a tower bottom extraction material 12 of the light component removal tower); (3) The mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol (a product 12 at the bottom of the light component removal tower) obtained at the bottom of the light component removal tower 5 is sent to a dealcoholization tower 13, the mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tertiary butyl ether (a product 20 at the bottom of the dealcoholization tower) is obtained at the bottom of the tower, the mixture of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol (a product 14 at the top of the dealcoholization tower) is obtained at the top of the tower, a part of the mixture is taken as a reflux 17 at the top of the dealcoholization tower after a reflux tank at the top of the dealcoholization tower, and a part of the mixture 18 of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol obtained at the top of the dealcoholization tower is partially extracted; (4) The mixture 18 of the propylene glycol primary mono-tertiary butyl ether, the C8 and the tertiary butyl alcohol is sent to a product refining tower 21, a product refining tower top extraction material 22 is obtained at the tower top, after passing through a product refining tower top reflux tank 24, part of the mixture is taken as a product refining tower top reflux 25, part of the mixture is taken as a mixture 26 of the tertiary butyl ether and the C8, and a propylene glycol primary mono-tertiary butyl ether product 28 is obtained at the tower bottom; (5) The mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether (the material 20 extracted from the bottom of the dealcoholization tower) obtained from the bottom of the dealcoholization tower is sent to an alcohol refining tower 29, the material 30 extracted from the top of the alcohol refining tower is obtained from the top of the alcohol refining tower, and after passing through a reflux tank 32 at the top of the alcohol refining tower, part of the material is taken as reflux 33 at the top of the alcohol refining tower, part of the material is taken as mixture 34 of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether, the material propylene glycol 36 extracted from the bottom of the alcohol refining tower is obtained from the bottom of the tower, and the material returns to the reactor 3.
Example 1
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor 3, and carrying out etherification reaction under the etherification reaction conditions: the reaction temperature is 50 ℃, the residence time is 150min, the alcohol-alkene ratio is 2:1, and the reaction pressure is 1.5MPa. The composition of the mixture obtained after the reaction was 20.48% by weight of propylene glycol, 61.49% by weight of mixed carbon, 14.23% by weight of propylene glycol primary mono-t-butyl ether, 1.40% by weight of propylene glycol Zhong Shanshu butyl ether, 1.21% by weight of propylene glycol di-t-butyl ether, 0.51% by weight of C and 0.68% by weight of t-butanol. And (3) sending the mixture obtained by the reaction into a light component removing tower 5, wherein the tower top pressure of the light component removing tower is 0.3MPa, the tower top temperature is 35 ℃, and the reflux ratio is 1:1. The unreacted mixed carbon four is obtained at the top of the dehydrogenation component tower, and the mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol, which is obtained at the bottom of the tower, is sent to a dealcoholization tower 13, the theoretical plate number of the dealcoholization tower is 40, the feed inlet is arranged at the 18 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 140 ℃, the tower bottom temperature is 185 ℃, and the reflux ratio is 1:1. The mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained at the bottom of the dealcoholization tower 13 is sent to an alcohol refining tower 29, the theoretical plate number of the alcohol refining tower is 30, the feeding port is arranged at the 20 th block, the temperature of the top of the tower is 140 ℃, the temperature of the bottom of the tower is 180 ℃, and the reflux ratio is 10:1. the mixture of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether is obtained at the top of the alcohol refining tower 29, and propylene glycol obtained at the bottom of the alcohol refining tower is recycled to the etherification reactor 3 for reaction. The mixture of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol obtained at the top of the dealcoholization tower 13 is sent to a product refining tower 21, the theoretical plate number of the product refining tower 21 is 25, a feed inlet is arranged at the 14 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 100 ℃, the tower bottom temperature is 150 ℃, and the reflux ratio is 20:1. The mixture of tertiary butanol and C8 is obtained at the top of the product refining tower, and the propylene glycol primary mono-tertiary butyl ether product is obtained at the bottom of the product refining tower.
Through chromatographic analysis, the purity of the propylene glycol primary mono-tertiary butyl ether at the bottom of the product refining tower reaches 99.95%, and the purity of the propylene glycol at the bottom of the alcohol refining tower reaches 99.4%. The single pass selectivity of propylene glycol primary mono-tertiary butyl ether was calculated to be 91.2%.
Example 2
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor 3, and carrying out etherification reaction under the etherification reaction conditions: the reaction temperature is 60 ℃, the residence time is 130min, the alcohol-alkene ratio is 3:1, and the reaction pressure is 1.2MPa. The composition of the mixture obtained after the reaction was 23.15wt% of propylene glycol, 56.65wt% of mixed carbon, 16.49wt% of propylene glycol primary mono-t-butyl ether, 1.63wt% of propylene glycol Zhong Shanshu butyl ether, 0.87wt% of propylene glycol di-t-butyl ether, 0.34wt% of C8 and 0.87wt% of t-butanol. And (3) sending the mixture obtained by the reaction into a light component removing tower 5, wherein the tower top pressure of the light component removing tower is 0.4MPa, the tower top temperature is 45 ℃, and the reflux ratio is 2:1. The unreacted mixed C four is obtained at the top of the dehydrogenation component tower, and the mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol, which is obtained at the bottom of the tower, is sent to a dealcoholization tower 13, the theoretical plate number of the dealcoholization tower is 50, a feed inlet is arranged at the 23 rd theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 142 ℃, the tower bottom temperature is 188 ℃, and the reflux ratio is 2:1. The mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained at the bottom of the dealcoholization tower is sent to an alcohol refining tower 29, the theoretical plate number of the alcohol refining tower is 40, the feeding port is arranged at the 260 th block, the temperature of the top of the tower is 145 ℃, the temperature of the bottom of the tower is 185 ℃, and the reflux ratio is 12:1. the mixture of the propylene glycol Zhong Shanshu butyl ether and the propylene glycol di-tert-butyl ether is obtained at the top of the alcohol refining tower, and the propylene glycol obtained at the bottom of the alcohol refining tower is recycled to the etherification reactor for reaction. The mixture of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol obtained from the top of the dealcoholization tower is sent to a product refining tower 21, the theoretical plate number of the product refining tower is 30, a feed inlet is arranged at the 16 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 105 ℃, the tower bottom temperature is 155 ℃, and the reflux ratio is 30:1. The mixture of tertiary butanol and C8 is obtained at the top of the product refining tower, and the propylene glycol primary mono-tertiary butyl ether product is obtained at the bottom of the product refining tower.
Through chromatographic analysis, the purity of the propylene glycol primary mono-tertiary butyl ether at the bottom of the product refining tower reaches 99.92%, and the purity of the propylene glycol at the bottom of the alcohol refining tower reaches 99.5%. The single pass selectivity of propylene glycol primary mono-tertiary butyl ether was calculated to be 91.5%.
Example 3
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor 3, and carrying out etherification reaction under the etherification reaction conditions: the reaction temperature is 65 ℃, the residence time is 120min, the alcohol-alkene ratio is 3.5:1, and the reaction pressure is 1.0MPa. The composition of the mixture obtained after the reaction was 27.13% by weight of propylene glycol, 46.79% by weight of mixed carbon, 23.56% by weight of propylene glycol primary mono-t-butyl ether, 2.01% by weight of propylene glycol Zhong Shanshu-butyl ether, 0.41% by weight of propylene glycol di-t-butyl ether, 0.011% by weight of C8.011% by weight and 0.089% by weight of t-butanol. And (3) sending the mixture obtained by the reaction into a light component removing tower 5, wherein the tower top pressure of the light component removing tower is 0.5MPa, the tower top temperature is 60 ℃, and the reflux ratio is 3:1. The unreacted mixed C four is obtained at the top of the dehydrogenation component tower, and the mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol, which is obtained at the bottom of the tower, is sent to a dealcoholization tower 13, the theoretical plate number of the dealcoholization tower is 60, a feed inlet is arranged at the 28 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 145 ℃, the tower bottom temperature is 190 ℃, and the reflux ratio is 3:1. The mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained at the bottom of the dealcoholization tower is sent to an alcohol refining tower 29, the theoretical plate number of the alcohol refining tower is 50, the feeding hole is arranged at the 32 th block, the tower top temperature is 150 ℃, the tower bottom temperature is 190 ℃, and the reflux ratio is 15:1. the mixture of the propylene glycol Zhong Shanshu butyl ether and the propylene glycol di-tert-butyl ether is obtained at the top of the alcohol refining tower, and the propylene glycol obtained at the bottom of the alcohol refining tower is recycled to the etherification reactor for reaction. The mixture of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol obtained from the top of the dealcoholization tower is sent to a product refining tower 21, the theoretical plate number of the product refining tower is 40, a feed inlet is arranged at the 21 st theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 110 ℃, the tower bottom temperature is 160 ℃, and the reflux ratio is 40:1. The mixture of tertiary butanol and C8 is obtained at the top of the product refining tower, and the propylene glycol primary mono-tertiary butyl ether product is obtained at the bottom of the product refining tower.
Through chromatographic analysis, the purity of the propylene glycol primary mono-tertiary butyl ether at the bottom of the product refining tower reaches 99.96%, and the purity of the propylene glycol at the bottom of the alcohol refining tower reaches 99.6%. The single pass selectivity of propylene glycol primary mono-tertiary butyl ether was calculated to be 90.5%.
Example 4
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor 3, and carrying out etherification reaction under the etherification reaction conditions: the reaction temperature is 70 ℃, the residence time is 110min, the alcohol-alkene ratio is 4:1, and the reaction pressure is 0.8MPa. The composition of the mixture obtained after the reaction was 37.15wt% of propylene glycol, 41.56wt% of mixed carbon, 19.12wt% of propylene glycol primary mono-t-butyl ether, 1.65wt% of propylene glycol Zhong Shanshu butyl ether, 0.35wt% of propylene glycol di-t-butyl ether, 0.105wt% of C, and 0.065wt% of t-butanol. And (3) feeding the mixture obtained by the reaction into a light component removing tower 5, wherein the tower top pressure of the light component removing tower is 0.6MPa, the tower top temperature is 70 ℃, and the reflux ratio is 4:1. The unreacted mixed C four is obtained at the top of the dehydrogenation component tower, and the mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol, which is obtained at the bottom of the tower, is sent to a dealcoholization tower 13, the theoretical plate number of the dealcoholization tower is 70, a feed inlet is arranged at the 33 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 148 ℃, the tower bottom temperature is 192 ℃, and the reflux ratio is 4:1. The mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained at the bottom of the dealcoholization tower is sent to an alcohol refining tower 29, the theoretical plate number of the alcohol refining tower is 60, the feeding hole is arranged at the 39 th block, the temperature of the top of the tower is 155 ℃, the temperature of the bottom of the tower is 195 ℃, and the reflux ratio is 18:1. the mixture of the propylene glycol Zhong Shanshu butyl ether and the propylene glycol di-tert-butyl ether is obtained at the top of the alcohol refining tower, and the propylene glycol obtained at the bottom of the alcohol refining tower is recycled to the etherification reactor for reaction. The mixture of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol obtained from the top of the dealcoholization tower is sent to a product refining tower 21, the theoretical plate number of the product refining tower is 50, a feed inlet is arranged at the 26 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 115 ℃, the tower bottom temperature is 165 ℃, and the reflux ratio is 50:1. The mixture of tertiary butanol and C8 is obtained at the top of the product refining tower, and the propylene glycol primary mono-tertiary butyl ether product is obtained at the bottom of the product refining tower.
Through chromatographic analysis, the purity of the propylene glycol primary mono-tertiary butyl ether at the bottom of the product refining tower reaches 99.99 percent, and the purity of the propylene glycol at the bottom of the alcohol refining tower reaches 99.7 percent. The single pass selectivity of propylene glycol primary mono-tertiary butyl ether was calculated to be 90.8%.
Example 5
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor 3, and carrying out etherification reaction under the etherification reaction conditions: the reaction temperature is 80 ℃, the residence time is 100min, the alcohol-alkene ratio is 5:1, and the reaction pressure is 0.5MPa. The composition of the mixture obtained after the reaction was 45.45wt% of propylene glycol, 37.54wt% of mixed carbon, 15.56wt% of propylene glycol primary mono-tert-butyl ether, 1.02wt% of propylene glycol Zhong Shanshu butyl ether, 0.33wt% of propylene glycol di-tert-butyl ether, 0.068wt% of C and 0.032wt% of tert-butanol. And (3) sending the mixture obtained by the reaction into a light component removing tower 5, wherein the tower top pressure of the light component removing tower is 0.45MPa, the tower top temperature is 50 ℃, and the reflux ratio is 5:1. The unreacted mixed C four is obtained at the top of the dehydrogenation component tower, and the mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol, which is obtained at the bottom of the tower, is sent to a dealcoholization tower 13, the theoretical plate number of the dealcoholization tower is 80, a feed inlet is arranged at the 38 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 150 ℃, the tower bottom temperature is 195 ℃, and the reflux ratio is 5:1. The mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained at the bottom of the dealcoholization tower is sent to an alcohol refining tower 29, the theoretical plate number of the alcohol refining tower is 50, the feeding hole is arranged at the 32 th block, the temperature of the top of the tower is 160 ℃, the temperature of the bottom of the tower is 200 ℃, and the reflux ratio is 20:1. the mixture of the propylene glycol Zhong Shanshu butyl ether and the propylene glycol di-tert-butyl ether is obtained at the top of the alcohol refining tower, and the propylene glycol obtained at the bottom of the alcohol refining tower is recycled to the etherification reactor for reaction. The mixture of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol obtained from the top of the dealcoholization tower is sent to a product refining tower 21, the theoretical plate number of the product refining tower is 60, a feed inlet is arranged at the position of the 32 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 120 ℃, the tower bottom temperature is 170 ℃, and the reflux ratio is 40:1. The mixture of tertiary butanol and C8 is obtained at the top of the product refining tower, and the propylene glycol primary mono-tertiary butyl ether product is obtained at the bottom of the product refining tower.
Through chromatographic analysis, the purity of the propylene glycol primary mono-tertiary butyl ether at the bottom of the product refining tower reaches 99.98%, and the purity of the propylene glycol at the bottom of the alcohol refining tower reaches 99.3%. The single pass selectivity of propylene glycol primary mono-tertiary butyl ether was calculated to be 92.1%.
Claims (12)
1. A process for preparing propylene glycol primary mono-tertiary butyl ether, the process comprising: (1) Fully mixing the raw materials with the carbon four and propylene glycol, and then sending the mixture into a reactor to carry out etherification reaction under the etherification reaction condition; (2) Sending the mixture obtained by the reaction into a light component removal tower, obtaining unreacted mixed carbon four at the top of the tower, and obtaining a mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol at the bottom of the tower; (3) Sending the mixture of propylene glycol, propylene glycol primary mono-tertiary butyl ether, propylene glycol Zhong Shanshu butyl ether, propylene glycol di-tertiary butyl ether, C8 and tertiary butanol obtained at the bottom of the light component removing tower into a dealcoholization tower, obtaining the mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tertiary butyl ether at the bottom of the dealcoholization tower, and obtaining the mixture of propylene glycol primary mono-tertiary butyl ether, C8 and tertiary butanol at the top of the dealcoholization tower; (4) Sending the mixture of the propylene glycol primary mono-tertiary butyl ether, the C8 and the tertiary butanol obtained from the top of the dealcoholization tower into a product refining tower, obtaining the mixture of the tertiary butanol and the C8 from the top of the tower, and obtaining the propylene glycol primary mono-tertiary butyl ether product from the bottom of the tower; (5) And (3) sending the mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained at the bottom of the dealcoholization tower into an alcohol refining tower, obtaining the mixture of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether at the top of the alcohol refining tower, and obtaining propylene glycol at the bottom of the alcohol refining tower.
2. The method according to claim 1, characterized in that: the etherification reaction conditions are as follows: the reaction temperature is 40-80 ℃, the residence time is 100-150min, the alcohol-alkene ratio is 2-5:1, and the reaction pressure is 0.5-1.5MPa.
3. The method according to claim 1, characterized in that: the pressure at the top of the light component removing tower is 0.3-0.6MPa, the temperature at the top of the tower is 35-70 ℃, and the reflux ratio is 1-5:1.
4. A method according to any one of claims 1-3, characterized in that: the theoretical plate number of the dealcoholization tower is 40-80, the feed inlet is arranged at the 18-38 th theoretical plate, the tower top pressure is normal pressure, the tower top temperature is 140-150 ℃, the tower bottom temperature is 185-195 ℃, and the reflux ratio is 1-5:1.
5. The method according to claim 4, wherein: the theoretical plate number of the product refining tower is 20-60; the feed inlet is arranged at the 11 th to 32 th theoretical plates; the pressure at the top of the tower is normal pressure, the temperature at the top of the tower is 100-120 ℃, the temperature at the bottom of the tower is 150-170 ℃, and the reflux ratio is 20-50:1.
6. The method according to claim 5, wherein: the theoretical plate number of the product refining tower is 25-50; the feed inlet is arranged at the theoretical plates of 14 th to 26 th.
7. The method according to claim 6, wherein: the theoretical plate number of the product refining tower is 30-40; the feed inlet is arranged at 16-21 theoretical plates.
8. The method according to claim 5, wherein: the theoretical plate number of the alcohol refining tower is 30-60, the feeding hole is arranged at the 20 th-40 th block, the temperature of the top of the tower is 140-160 ℃, the temperature of the bottom of the tower is 180-200 ℃, and the reflux ratio is 10-20:1.
9. a method according to any one of claims 1-3, characterized in that: and the propylene glycol obtained at the bottom of the alcohol refining tower is recycled to the etherification reactor for reaction.
10. The preparation device of propylene glycol primary mono-tertiary butyl ether is characterized by comprising an etherification reactor, a light component removing tower, a dealcoholization tower, a product refining tower and an alcohol refining tower which are sequentially connected, wherein the light component removing tower, the dealcoholization tower, the product refining tower and the alcohol refining tower respectively comprise a tower top condenser, a reflux tank, a tower bottom reboiler, a feed inlet, a tower top discharge port and a tower bottom discharge port, the etherification reactor is provided with the feed inlet and the discharge port, the discharge port of the etherification reactor is connected with the feed inlet of the light component removing tower through a pipeline, the discharge port of the tower bottom of the light component removing tower is connected with the feed inlet of the dealcoholization tower through a pipeline, the discharge port of the tower top reflux tank is connected with the feed inlet of the product refining tower through a pipeline, and the discharge port of the tower bottom of the dealcoholization tower is connected with the feed inlet of the alcohol refining tower through a pipeline.
11. The apparatus according to claim 10, wherein: and a discharge hole at the bottom of the alcohol refining tower is connected with a feed inlet of the etherification reactor through a pipeline.
12. The apparatus according to claim 10 or 11, characterized in that: the top discharge port of the product refining tower is connected with a mixture product intermediate tank of C8 and tertiary butanol; and a mixture product intermediate tank of the propylene glycol Zhong Shanshu butyl ether and the propylene glycol di-tert-butyl ether is connected with a top discharge port of the alcohol refining tower.
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| US4675082A (en) * | 1986-09-22 | 1987-06-23 | Atlantic Richfield Company | Recovery of propylene glycol mono t-butoxy ether |
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| CN105985215A (en) * | 2015-02-12 | 2016-10-05 | 天津海成能源工程技术有限公司 | Cracking system for preparing high-purity isobutene from propylene glycol tert-butyl ether |
| CN106397137A (en) * | 2015-07-27 | 2017-02-15 | 万华化学集团股份有限公司 | Method for preparing diol mono-tert-butyl ether |
| CN107778123A (en) * | 2017-10-23 | 2018-03-09 | 黄河三角洲京博化工研究院有限公司 | A kind of method for preparing isobutene |
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| US4675082A (en) * | 1986-09-22 | 1987-06-23 | Atlantic Richfield Company | Recovery of propylene glycol mono t-butoxy ether |
| CN104311398A (en) * | 2014-09-20 | 2015-01-28 | 江苏怡达化学股份有限公司 | Synthetic method of propanediol butyl ether and dipropylene glycol butyl ether |
| CN105985215A (en) * | 2015-02-12 | 2016-10-05 | 天津海成能源工程技术有限公司 | Cracking system for preparing high-purity isobutene from propylene glycol tert-butyl ether |
| CN106397137A (en) * | 2015-07-27 | 2017-02-15 | 万华化学集团股份有限公司 | Method for preparing diol mono-tert-butyl ether |
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