CN112920025B - 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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- CN112920025B CN112920025B CN201911236124.9A CN201911236124A CN112920025B CN 112920025 B CN112920025 B CN 112920025B CN 201911236124 A CN201911236124 A CN 201911236124A CN 112920025 B CN112920025 B CN 112920025B
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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
- 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, a dealcoholization tower, a product refining tower and an alcohol refining tower for separation in sequence, sending the mixture obtained by the top of the alcohol refining tower into a cracking reactor for cracking reaction, sending the mixture obtained by the cracking reaction into a rectifying tower for separation, obtaining high-purity isobutene at the top of the tower, and obtaining propylene glycol at the bottom of the tower. The method has mild reaction conditions, safe and environment-friendly process, and the purity of the propylene glycol primary mono-tertiary butyl ether reaches more than 99.9% through separation, and the byproducts propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tertiary butyl ether can be prepared into high-purity isobutene through reaction and pyrolysis for recycling, so that the total selectivity of the propylene glycol primary mono-tertiary butyl ether reaches more than 99%.
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 for preparing propylene glycol primary mono-tertiary butyl ether with high conversion rate and high selectivity, can effectively separate a reaction mixture, and obtains 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) Separating the mixture obtained by the reaction in a light component removing 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 for separation, 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 for refining, 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) 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 for refining, 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; (6) Sending a mixture of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained from the top of the alcohol refining tower into a cracking reactor, and carrying out cracking reaction under the cracking reaction condition; (7) And directly returning the mixture obtained by the cracking reaction to an etherification reactor for reaction and/or sending the mixture to a rectifying tower for separation, obtaining high-purity isobutene at the top of the rectifying tower, and obtaining propylene glycol at the bottom of the rectifying 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 invention, the selected reactor is a fixed bed reactor, and the catalyst is macroporous strong acid cation exchange resin. In the invention, the composition of the selected mixed carbon four is 30-40wt% of isobutane, 10-20wt% of normal butene, 10-20wt% of normal butane, 10-20wt% of isobutene, 10-20wt% of fumaric acid, 5-15wt% of normal butene, 0.01-0.1wt% of carbon three and 0.1-0.5wt% of butadiene.
In the present invention, in order to control the conversion and selectivity of the reaction, the reaction must be controlled under reaction conditions such as a proper reaction temperature, residence time, alcohol-to-olefin ratio, and reaction pressure. 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 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 still more 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, the cracking reaction pressure is 0.05-0.1MPa, preferably 0.06-0.1MPa, more preferably 0.07-0.1MPa, and even more preferably 0.08-0.1MPa; the temperature is 140-160deg.C, preferably 142-158 deg.C, more preferably 145-155 deg.C, and even more preferably 148-152 deg.C; the residence time is from 0.5 to 1h, preferably from 0.6 to 1h, more preferably from 0.7 to 1h, still more preferably from 0.8 to 1h.
In the present invention, the catalyst for the cleavage reaction may be selected from solid acid catalysts such as acidic ion exchange resin catalysts, acidic supported molecular sieves, etc. The outlet material of the cracking reactor can be directly returned to the etherification reactor for recycling, high-purity isobutene and propylene glycol can be obtained through rectification, both the high-purity isobutene and the propylene glycol can be returned to the etherification reactor for recycling, and the high-purity isobutene product can be sold or utilized independently.
In the invention, the top pressure of the rectifying tower is 0.3-0.6MPa, preferably 0.32-0.58MPa, more preferably 0.35-0.55MPa, more preferably 0.35-0.52MPa, more preferably 0.35-0.50MPa, more preferably 0.35-0.48MPa, more preferably 0.38-0.45MPa, and further preferably 0.38-0.42MPa; the temperature of the tower top is 32-65 ℃, preferably 35-62 ℃, more preferably 38-60 ℃, more preferably 40-58 ℃, more preferably 40-55 ℃, more preferably 40-52 ℃, and more preferably 42-50 ℃; the bottom temperature is 210-230 ℃, preferably 212-228 ℃, more preferably 215-225 ℃, and further preferably 218-222 ℃; the reflux ratio is 1-5:1, preferably 1.5-4.5:1, more preferably 2-4:1, more preferably 2-3.5:1, and even more preferably 2-3:1.
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, high-purity isobutene obtained from the top of the rectifying tower is recycled to the etherification reactor for reaction, and propylene glycol obtained from the bottom of the rectifying tower is recycled to the etherification reactor for reaction.
According to another aspect of the present invention, there is provided a propylene glycol primary mono-tertiary butyl ether production apparatus, characterized in that the apparatus comprises an etherification reactor, a light component removal column, a dealcoholization column, a product refining column, an alcohol refining column, a cracking reactor and optionally a rectifying column which are connected in this order, the light component removal column, the dealcoholization column, the product refining column, the alcohol refining column and the rectifying column each comprise a top condenser, a reflux tank, a bottom reboiler, a feed port, a top discharge port and a bottom discharge port, the etherification reactor and the cracking reactor are respectively provided with a feed port and a discharge port, the etherification reactor discharge port is connected with the light component removal column feed port through a pipeline, the dealcoholization column discharge port is connected with the top reflux tank through a pipeline, the dealcoholization column discharge port is connected with the product refining column feed port through a pipeline, the alcohol column top discharge port is connected with the alcohol refining column feed port through a pipeline, and the etherification reactor discharge port is connected with the reflux tank through a pipeline, or the etherification reactor discharge port is connected with the reflux tank feed port through a pipeline, and the reactor is connected with the inlet/discharge port.
"optional" means that the subsequent device or step may or may not be present. In the case of a cleavage reactor whose outlet is connected to the inlet of the etherification reactor exclusively via a line, there may be no rectification column.
Preferably, the bottom discharge port of the alcohol refining tower is connected with the feed port of the etherification reactor through a pipeline.
More preferably, the top discharge port of the rectifying tower is connected with the top reflux tank through a pipeline, the discharge port of the top reflux tank is connected with the feed inlet of the etherification reactor through a pipeline, and the bottom discharge port is connected with the feed inlet of the etherification reactor through a pipeline.
The invention provides a preparation and separation method for preparing propylene glycol primary mono-tertiary butyl ether, which has high single-pass selectivity of propylene glycol primary mono-tertiary butyl ether of more than 95%, wherein the single-pass selectivity of 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 reaches more than 99.9% through separation, and the byproducts propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tertiary butyl ether can be prepared into high-purity isobutene through reaction and pyrolysis for recycling, so that the total selectivity of the propylene glycol primary mono-tertiary butyl ether reaches more than 99%.
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 propylene glycol primary mono-t-butyl ether, t-butanol and C8, 8 is a light component removal column top reflux drum, 9 is a light component removal column top reflux, 10 is a light component column top withdrawal, 11 is a light component removal column bottom reboiler, 12 is a light component removal column bottom withdrawal, 13 is a dealcoholization column, 14 is a dealcoholization column top withdrawal, 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-t-butyl ether, t-butanol and C8, 19 is a dealcoholization column bottom reboiler, 20 is a dealcoholization column bottom withdrawal, 21 is a product refining column, 22 is a product refining column top withdrawal, 23 is a product refining column top condenser, 24 is the top reflux drum of the product refining column, 25 is the top reflux drum of the product refining column, 26 is the mixture of tert-butyl alcohol and C8, 27 is the bottom reboiler of the product refining column, 28 is the primary mono-tert-butyl ether of propylene glycol, 29 is the alcohol refining column, 30 is the top reflux drum of the alcohol refining column, 31 is the top condenser of the alcohol refining column, 32 is the top reflux drum of the alcohol refining column, 33 is the top reflux drum of the alcohol refining column, 34 is the mixture of by-product propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether, 35 is the bottom reboiler of the alcohol refining column, 36 is the propylene glycol of the bottom of the alcohol refining column, 37 is the cleavage reactor, 38 is the mixture obtained after cleavage, 39 is the rectifying column, 40 is the top reflux drum of the rectifying column, 41 is the top condenser of the rectifying column, 42 is the top reflux drum of the rectifying column, 43 is the reflux drum of the isobutene, 44 is the bottom reboiler of the rectifying column, 46 is propylene glycol extracted from the bottom of the rectifying tower.
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 FIG. 1, the invention provides a preparation device of propylene glycol primary mono-tertiary butyl ether, the device comprises an etherification reactor 3, a light component removal tower 5, a dealcoholization tower 13, a product rectification tower 21, an alcohol refining tower 29, a cracking reactor 37 and a rectification tower 39 which are sequentially connected, the light component removal tower 5, the dealcoholization tower 13, the product rectification tower 21, the alcohol refining tower 29 and the rectification tower 39 respectively comprise a tower top condenser (7,15,23,31,41), a reflux tank (8,16,24,32,42), a tower bottom reboiler (11,19,27,35,45), a feed port, a tower top discharge port and a tower bottom discharge port, the etherification reactor 3 and the cracking reactor 37 are respectively 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 removal tower 5 through a pipeline, the discharge port of the light component removal tower 5 is connected with the feed port of the dealcoholization tower 13 through a pipeline, the discharge port of the dealcoholization tower 13 is connected with a 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 rectification tower 21 through a pipeline, the discharge port of the dealcoholization tower 13 is connected with the feed port of the rectification tower top 29 through a pipeline, the reflux tank 37 is connected with the feed port of the etherification reactor 3 through a pipeline 32, and the feed port is connected with the feed port of the reflux tank 32 through the reflux tank is connected with the feed port of the etherification reactor 3.
Preferably, the bottom discharge port of the alcohol refining tower 29 is connected with the feed port of the etherification reactor 3 through a pipeline.
More preferably, the top outlet of the rectifying tower 39 is connected with the top reflux tank 42 through a pipeline, the outlet of the top reflux tank is connected with the feed inlet of the etherification reactor through a pipeline, and the bottom outlet is connected with the feed inlet of the etherification reactor 3 through a pipeline.
The method for preparing the propylene glycol primary mono-tertiary butyl ether with high conversion rate and high selectivity comprises the following steps:
(1) Fully mixing raw materials with carbon number four 1 and propylene glycol 2, and then sending the mixture into an etherification reactor 3, and carrying out etherification reaction under the etherification reaction condition;
(2) Separating the mixture 4 after reaction in a light component removing tower 5, obtaining unreacted mixed carbon four 6 at the top of the tower, taking the rear part of the mixture as the top reflux 9 of the light component removing tower through a reflux tank 8, taking the rear part of the mixture as the top reflux 10 of the light component removing tower, and obtaining 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 at the bottom of the tower (a material 12 is taken at the bottom of the light component removing 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 butyl alcohol obtained at the bottom of the light component removing tower into a dealcoholizing tower 13 for separation, obtaining a mixture of propylene glycol, propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tertiary butyl ether (a material 20 extracted from the bottom of the dealcoholizing tower) at the bottom of the tower, and taking a part of a material 14 extracted from the top of the dealcoholizing tower as a reflux 17 at the top of the dealcoholizing tower after passing through a reflux tank 16, and partially extracting to obtain a mixture 18 of propylene glycol primary mono-tertiary butyl ether, tertiary butyl alcohol and C8;
(4) Sending the mixture 18 of the propylene glycol primary mono-tertiary butyl ether, tertiary butyl alcohol and C8 obtained from the top of the dealcoholization tower into a product refining tower 21 for refining, wherein part of a material 22 extracted from the top of the product refining tower 21 is used as a product refining tower top reflux 25 after passing through a reflux tank 24, part of the material is extracted to obtain a mixture 26 of tertiary butyl alcohol and C8, and the propylene glycol primary mono-tertiary butyl ether product 28 is obtained from the bottom of the product refining tower;
(5) 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 13 into an alcohol refining tower 29 for refining, wherein part of a material 30 extracted from the top of the alcohol refining tower is used as a reflux 33 at the top of the alcohol refining tower after passing through a reflux tank 32, part of the material is extracted to obtain a mixture 34 of byproduct propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether, and propylene glycol (a material propylene glycol 36 extracted from the bottom of the alcohol refining tower) is obtained at the bottom of the tower;
(6) Sending a mixture 34 of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained from the top of the alcohol refining tower 29 into a cracking reactor 37, and carrying out cracking reaction under cracking reaction conditions;
(7) The mixture obtained by the cracking reaction is directly returned to the etherification reactor 3 or is sent to the rectifying tower 39 for separation, the material 40 extracted from the top of the rectifying tower is partially taken as the reflux 43 at the top of the rectifying tower after passing through the reflux tank 42, the isobutene 44 with high purity obtained by partial extraction is returned to the etherification reactor 3, and the propylene glycol obtained from the bottom of the rectifying tower (propylene glycol 46 extracted from the bottom of the rectifying tower) is returned to the etherification 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, 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, 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 C four is obtained at the top of the dehydrogenation component tower, 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 bottom of the tower and is sent to a dealcoholization tower, the theoretical plate number of the dealcoholization tower is 40, a 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 is sent into an alcohol refining tower, 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 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 into a product refining tower, the theoretical plate number of the product refining tower 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. And (3) sending 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 into a cracking reactor, and carrying out cracking reaction under the cracking reaction condition, wherein the cracking reaction pressure is 0.05Mpa, the temperature is 140 ℃, and the residence time is 0.5h. And (3) sending the mixture obtained by the cracking reaction into a rectifying tower for separation, wherein the top pressure of the rectifying tower is 0.3MPa, the top temperature of the rectifying tower is 32 ℃, the bottom temperature of the rectifying tower is 210 ℃, and the reflux ratio is 1:1. The high-purity isobutene is obtained at the top of the rectifying tower, the propylene glycol is obtained at the bottom of the rectifying tower, and the high-purity isobutene is obtained at the top of the rectifying tower, and the propylene glycol is obtained at the bottom of the rectifying tower and is recycled to the etherification reactor for reaction.
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%, the purity of the propylene glycol at the bottom of the alcohol refining tower reaches 99.4%, and the purity of the isobutene obtained at the top of the rectifying tower reaches 99.5%. The single pass selectivity of the propylene glycol primary mono-tertiary butyl ether is calculated to be 91.2%, and the total selectivity of the propylene glycol primary mono-tertiary butyl ether reaches 99.5%.
Example 2
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor, 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, 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, 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 into a dealcoholization tower, 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 into an alcohol refining tower, the theoretical plate number of the alcohol refining tower is 40, the feeding hole 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 into a product refining tower, 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. And (3) sending 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 into a cracking reactor, and carrying out cracking reaction under the cracking reaction condition, wherein the cracking reaction pressure is 0.06Mpa, the temperature is 145 ℃, and the residence time is 0.6h. And (3) sending the mixture obtained by the cracking reaction into a rectifying tower for separation, wherein the top pressure of the rectifying tower is 0.4MPa, the top temperature of the rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 215 ℃, and the reflux ratio is 2:1. The high-purity isobutene is obtained at the top of the rectifying tower, the propylene glycol is obtained at the bottom of the rectifying tower, and the high-purity isobutene is obtained at the top of the rectifying tower, and the propylene glycol is obtained at the bottom of the rectifying tower and is recycled to the etherification reactor for reaction.
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%, the purity of the propylene glycol at the bottom of the alcohol refining tower reaches 99.5%, and the purity of the isobutene obtained at the top of the rectifying tower reaches 99.4%. The single pass selectivity of the propylene glycol primary mono-tertiary butyl ether is calculated to be 91.5%, and the total selectivity of the propylene glycol primary mono-tertiary butyl ether reaches 99.4%.
Example 3
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor, 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, 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, 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 into a dealcoholization tower, 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 into an alcohol refining tower, 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 150 ℃, the temperature of the bottom of the tower 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 into a product refining tower, 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. And (3) sending 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 into a cracking reactor, and carrying out cracking reaction under the cracking reaction condition, wherein the cracking reaction pressure is 0.08Mpa, the temperature is 150 ℃, and the residence time is 0.8h. And (3) sending the mixture obtained by the cracking reaction into a rectifying tower for separation, wherein the top pressure of the rectifying tower is 0.45MPa, the top temperature of the rectifying tower is 50 ℃, the bottom temperature of the rectifying tower is 220 ℃, and the reflux ratio is 3:1. The high-purity isobutene is obtained at the top of the rectifying tower, the propylene glycol is obtained at the bottom of the rectifying tower, and the high-purity isobutene is obtained at the top of the rectifying tower, and the propylene glycol is obtained at the bottom of the rectifying tower and is recycled to the etherification reactor for reaction.
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%, the purity of the propylene glycol at the bottom of the alcohol refining tower is 99.6%, and the purity of the isobutene obtained at the top of the rectifying tower is 99.3%. The single pass selectivity of the propylene glycol primary mono-tertiary butyl ether is calculated to be 90.5%, and the total selectivity of the propylene glycol primary mono-tertiary butyl ether reaches 99.7%.
Example 4
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor, 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) sending the mixture obtained by the reaction into a light component removing tower, 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 into a dealcoholization tower, 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, 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 into a product refining tower, 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. And (3) sending 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 into a cracking reactor, and carrying out cracking reaction under the cracking reaction condition, wherein the cracking reaction pressure is 0.09Mpa, the temperature is 155 ℃, and the residence time is 0.9h. And (3) sending the mixture obtained by the cracking reaction into a rectifying tower for separation, wherein the top pressure of the rectifying tower is 0.5MPa, the top temperature of the rectifying tower is 60 ℃, the bottom temperature of the rectifying tower is 225 ℃, and the reflux ratio is 4:1. The high-purity isobutene is obtained at the top of the rectifying tower, the propylene glycol is obtained at the bottom of the rectifying tower, and the high-purity isobutene is obtained at the top of the rectifying tower, and the propylene glycol is obtained at the bottom of the rectifying tower and is recycled to the etherification reactor for reaction.
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%, the purity of the propylene glycol at the bottom of the alcohol refining tower reaches 99.7%, and the purity of the isobutene obtained at the top of the rectifying tower reaches 99.6%. The single pass selectivity of the propylene glycol primary mono-tertiary butyl ether is calculated to be 90.8%, and the total selectivity of the propylene glycol primary mono-tertiary butyl ether reaches 99.6%.
Example 5
Fully mixing the raw materials with the carbon four and the propylene glycol, and then sending the mixture into a reactor, 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, 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, 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 bottom of the tower and is sent to a dealcoholization tower, 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 into an alcohol refining tower, 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 into a product refining tower, the theoretical plate number of the product refining tower is 60, a feed inlet is arranged at 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. And (3) sending 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 into a cracking reactor, and carrying out cracking reaction under the cracking reaction condition, wherein the cracking reaction pressure is 0.1Mpa, the temperature is 160 ℃, and the residence time is 1h. And (3) sending the mixture obtained by the cracking reaction into a rectifying tower for separation, wherein the top pressure of the rectifying tower is 0.6MPa, the top temperature of the rectifying tower is 65 ℃, the bottom temperature of the rectifying tower is 230 ℃, and the reflux ratio is 5:1. The high-purity isobutene is obtained at the top of the rectifying tower, the propylene glycol is obtained at the bottom of the rectifying tower, and the high-purity isobutene is obtained at the top of the rectifying tower, and the propylene glycol is obtained at the bottom of the rectifying tower and is recycled to the etherification reactor for reaction.
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%, the purity of the propylene glycol at the bottom of the alcohol refining tower is 99.3%, and the purity of the isobutene obtained at the top of the rectifying tower is 99.7%. The single pass selectivity of the propylene glycol primary mono-tertiary butyl ether is 92.1 percent, and the total selectivity of the propylene glycol primary mono-tertiary butyl ether reaches 99.8 percent.
Claims (13)
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) Separating the mixture obtained by the reaction in a light component removing 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 for separation, 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 for refining, 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) 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 for refining, 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; (6) Sending a mixture of propylene glycol Zhong Shanshu butyl ether and propylene glycol di-tert-butyl ether obtained from the top of the alcohol refining tower into a cracking reactor, and carrying out cracking reaction under the cracking reaction condition; (7) And directly returning the mixture obtained by the cracking reaction to an etherification reactor for reaction and/or sending the mixture to a rectifying tower for separation, obtaining high-purity isobutene at the top of the rectifying tower, and obtaining propylene glycol at the bottom of the rectifying 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: the pressure of the cracking reaction is 0.05-0.1Mpa, the temperature is 140-160 ℃, and the residence time is 0.5-1h.
10. The method according to claim 9, wherein: the top pressure of the rectifying tower is 0.3-0.6MPa, the top temperature is 32-65 ℃, the bottom temperature is 210-230 ℃, and the reflux ratio is 1-5:1.
11. 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, the high-purity isobutene obtained at the top of the rectifying tower is recycled to the etherification reactor for reaction, and the propylene glycol obtained at the bottom of the rectifying tower is recycled to the etherification reactor for reaction.
12. The preparation device of propylene glycol primary tert-butyl ether is characterized by comprising an etherification reactor, a light component removal tower, a dealcoholization tower, a product refining tower, an alcohol refining tower, a cracking reactor and an optional rectifying tower which are sequentially connected, wherein each of the light component removal tower, the dealcoholization tower, the product refining tower, the alcohol refining tower and the rectifying 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 and the cracking reactor are respectively 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 light component removal tower bottom discharge port is connected with the dealcoholization tower feed port through a pipeline, the tower top discharge port is connected with the tower top reflux tank through a pipeline, the tower top discharge port is connected with the alcohol refining tower feed port through a pipeline, and the tower top reflux tank discharge port is connected with the cracking reactor feed port through a pipeline, and the etherification reactor feed port is connected with the rectifying tower feed port or the rectifying tower feed port through a pipeline.
13. The device for preparing propylene glycol primary mono-tertiary butyl ether according to claim 12, wherein the outlet at the bottom of the alcohol refining tower is connected with the inlet of the etherification reactor through a pipeline; and/or the number of the groups of groups,
the top discharge port of the rectifying tower is connected with the top reflux tank through a pipeline, the discharge port of the top reflux tank is connected with the feed inlet of the etherification reactor through a pipeline, and the bottom discharge port is connected with the feed inlet of the etherification reactor through a pipeline.
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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 |
| 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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