CN105218305A - A kind of byproduct recovery process of synthetic gas preparing ethylene glycol - Google Patents
A kind of byproduct recovery process of synthetic gas preparing ethylene glycol Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The present invention relates to a kind of byproduct recovery process of synthetic gas preparing ethylene glycol, this recovery process is reclaimed methyl alcohol, ethanol and methyl glycolate by 1# methanol distillation column, de-ester tower, 2# methanol distillation column, film recovery assembly and ester recovery tower, obtain the azeotrope of 1,2-butyleneglycol and ethylene glycol as frostproofer raw material at the tower top of product tower simultaneously.Recovery process of the present invention can realize, to the recycling of byproduct, obviously reducing raw materials cost, increases economic benefit, reduces discharge of wastewater, be conducive to environment protection, and whole process device structure is simple, easy for installation, energy consumption is low, better economic benefit.
Description
Technical field
The invention belongs to coal chemical technology, be specifically related to a kind of byproduct recovery process of synthetic gas preparing ethylene glycol.
Background technology
Can produce methyl alcohol, ethanol, 1,2-butyleneglycol and some Esters in coal-ethylene glycol technique in prior art, being recovered in the operational path of existing coal-ethylene glycol of these byproducts all has no report, causes great waste to raw material.Therefore, the present invention mainly studies the byproduct recovery process of synthetic gas preparing ethylene glycol.
Patent CN101928201A discloses a kind of purifying technique of coal glycol rude products, this purifying technique route by saponification reaction, go methyl alcohol, hydrogenation reaction, three-tower rectification and adsorption treatment, obtained premium grads ethylene glycol product of purifying from coal glycol rude products.This patent operational path only relates to the recovery to a part of methyl alcohol, has no the report reclaimed the ethanol in raw material and Ester.
Patent CN103664516A relates to a kind of ethylene glycol separating technology of synthetic gas preparing ethylene glycol, use valerone as entrainer in this technique, azeotropic distillation is carried out with the thick ethylene glycol obtained through the de-ester pre-treatment of Methanol Recovery/dehydration, obtain the azeotrope being rich in ethylene glycol, the described azeotrope being rich in ethylene glycol is carried out condensation separation obtain being rich in the liquid phase of entrainer and be rich in the liquid phase of ethylene glycol product, the liquid phase being rich in ethylene glycol product carries out refining further obtaining premium grads ethylene glycol and salable product ethylene glycol again.This route uses azeotropic distillation to come separating ethylene glycol and 1,2-butyleneglycol, increases energy consumption, and has no its further recovery to byproduct in this route.
Summary of the invention
The object of the present invention is to provide a kind of byproduct recovery process of synthetic gas preparing ethylene glycol.This recovery process is reclaimed methyl alcohol, ethanol and methyl glycolate by 1# methanol distillation column, de-ester tower, 2# methanol distillation column, film recovery assembly and ester recovery tower, obtain the azeotrope of 1,2-butyleneglycol and ethylene glycol as frostproofer raw material at the tower top of product tower simultaneously.
In order to the object that the byproduct realizing above-mentioned synthetic gas preparing ethylene glycol reclaims, the present invention adopts following technical scheme: the byproduct recovery process providing a kind of synthetic gas preparing ethylene glycol, it is characterized in that the concrete steps of this recovery process are:
The first step, in the middle part of the ethylene glycol thick product introduction 1# methanol distillation column of synthetic gas preparing ethylene glycol, 1# Methanol Recovery column overhead extraction non-condensable gas after condensation, byproduct methyl alcohol is reclaimed at 1# methanol distillation column side line, this step reclaims the byproduct methyl alcohol that the purity obtained is more than or equal to 99.5%, and the byproduct methyl alcohol of recovery can as raw material for synthesizing section; The tower reactor solution of 1# methanol distillation column sends into de-ester tower middle and upper part; Described 1# methanol distillation column is totally 20 ~ 55 pieces of theoretical stages, and working pressure is 80kPa ~ 120kPa, and the position that side is adopted is 4th ~ 6 pieces of theoretical stages, and still temperature is 60 ~ 130 DEG C;
Second step, introduce the tower reactor solution of the first step 1# methanol distillation column in de-ester tower middle and upper part after, de-ester column overhead steam refluxes after condensation, and extraction fusel, water and Ester, this fusel, water and Ester send into the middle part of 2# methanol distillation column; Described de-ester tower totally 35 ~ 55 pieces of theoretical stages, working pressure is 10kPa ~ 20kPa, and de-ester tower liquid feeding position is the position, middle and upper part of whole de-ester tower, and still temperature is 140 ~ 165 DEG C;
3rd step, enters the tower top solution of the de-ester tower at the middle part of 2# methanol distillation column, is more than or equal to the byproduct methyl alcohol of 99.5% in the overhead extraction purity of 2# methanol distillation column, and this byproduct methyl alcohol supplies synthesizing section reuse as raw material; The mixture of 2# methanol distillation column side take-off second alcohol and water, the mixture of this second alcohol and water enters film and reclaims assembly; The tower reactor solution of 2# methanol distillation column sends into ester recovery tower; Described 2# methanol distillation column is totally 35 ~ 55 pieces of theoretical stages, the medium position place of working pressure to be the liquid feeding position of 80kPa ~ 120kPa, 2# methanol distillation column be whole 2# methanol distillation column, and still temperature is 80 ~ 105 DEG C;
4th step, the mixture entering the second alcohol and water in film recovery assembly through the 3rd stepping processes in film recovery assembly, reclaims and obtains alcohol by-products;
5th step, sends into the 2# methanol distillation column tower reactor solution in ester recovery tower through the 3rd step, reclaims the Ester obtaining methyl glycolate, at ester recovery tower overhead extraction waste water in the tower reactor of ester recovery tower; Described ester recovery tower is totally 25 ~ 45 pieces of theoretical stages, and working pressure is 80kPa ~ 120kPa, and the liquid feeding position of ester recovery tower is the medium position place of whole ester recovery tower, and still temperature is 120 ~ 155 DEG C.
Compared with prior art, the present invention has following features:
(1) byproduct of the synthetic gas preparing ethylene glycol in the present invention is the methyl alcohol and N that are obtained by synthetic gas
2o
4synthesis methyl nitrite, recycling methyl nitrite and CO carry out carbonylation reaction and obtain dimethyl oxalate, and dimethyl oxalate obtains through Hydrogenation and produces in the process of ethylene glycol.To the recycling of byproduct, mainly through 1# methanol distillation column, 2# methanol distillation column, film recovery assembly and ester recovery tower four equipment, fusel, water, methyl glycolate are reclaimed, and the rate of recovery of byproduct is higher.Byproduct is recycled, obviously reduces raw materials cost, increase economic benefit, reduce discharge of wastewater, be conducive to environment protection.
(2) reclaim film that ethanol selects in the present invention to reclaim assembly and have the advantages that flow process is short, Operation and Maintenance simple, plant area is less, and device structure is simple, easy for installation, energy consumption is low, further increase the economic benefit of production.
Accompanying drawing explanation
The byproduct recovery process schema of the synthetic gas preparing ethylene glycol in Fig. 1 the present invention.
In figure, the thick product of 1-ethylene glycol, 2-byproduct methyl alcohol (or methyl alcohol), 3-non-condensable gas, 4-premium grads ethylene glycol, 5-1, the azeotrope of 2-butyleneglycol and ethylene glycol, 6-heavy constituent, the mixture of 7-second alcohol and water, 8-alcohol by-products, the Esters such as 9-methyl glycolate, 10-waste water, 11-1# methanol distillation column, 12-takes off ester tower, 13-product tower, 14-2# methanol distillation column, 15-film reclaims assembly, 16-ester recovery tower, 17-pump, 18-reboiler, 19-return tank, 20-condenser, 21-vacuumizes, 22-fusel, water and Ester.
Embodiment
The present invention is further described below in conjunction with embodiment and accompanying drawing thereof.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.Should be understood that those skilled in the art can make various changes or modifications the present invention after having read content of the present invention in addition, these equivalent form of values fall within the protection domain that the application's claim limits equally.
The concrete steps of the byproduct recovery process (being called for short recovery process, see Fig. 1) of synthetic gas preparing ethylene glycol of the present invention are:
The first step, the thick product 1 of ethylene glycol of synthetic gas preparing ethylene glycol enters in the middle part of 1# methanol distillation column 11, the a small amount of non-condensable gas 3 of 1# methanol distillation column 11 tower top extraction after condensation, byproduct methyl alcohol 2 is reclaimed at 1# methanol distillation column 11 side line, this step reclaims the byproduct methyl alcohol (this purity refers to the massfraction of the middle methyl alcohol reclaiming the methanol solution obtained) that the purity obtained is more than or equal to 99.5%, and the byproduct methyl alcohol of recovery can prepare methyl nitrite as raw material for synthesizing section; The tower reactor solution of 1# methanol distillation column 11 sends into de-ester tower 12 middle and upper part; Described 1# methanol distillation column 11 is totally 20 ~ 55 pieces of theoretical stages, and working pressure is 80kPa ~ 120kPa, and the position that side is adopted is 4th ~ 6 pieces of theoretical stages, and still temperature is 60 ~ 130 DEG C;
Second step, introduce the tower reactor solution of the first step 1# methanol distillation column 11 in de-ester tower 12 middle and upper part after, de-ester tower 12 overhead vapours refluxes after condensation, and extraction fusel, water and Ester 22, this fusel, water and Ester 22 sends into the middle part of 2# methanol distillation column 14; Described de-ester tower 12 totally 35 ~ 55 pieces of theoretical stages, working pressure is 10kPa ~ 20kPa, and de-ester tower 12 liquid feeding position is the position, middle and upper part of whole de-ester tower 12, and still temperature is 140 ~ 165 DEG C;
3rd step, enter the tower top solution of the de-ester tower 12 at the middle part of 2# methanol distillation column 14, be more than or equal to the byproduct methyl alcohol of 99.5% in the overhead extraction purity of 2# methanol distillation column 14, this byproduct methyl alcohol prepares methyl nitrite reuse as raw material for synthesizing section; The mixture 7 of 2# methanol distillation column 14 side take-off second alcohol and water, and the mixture 7 of this second alcohol and water is sent into film recovery assembly 15; The tower reactor solution of 2# methanol distillation column 14 sends into ester recovery tower 16; Described 2# methanol distillation column 14 is totally 35 ~ 55 pieces of theoretical stages, the medium position place of working pressure to be the liquid feeding position of 80kPa ~ 120kPa, 2# methanol distillation column 14 be whole 2# methanol distillation column 14, and still temperature is 80 ~ 105 DEG C;
4th step, the mixture 7 entering the second alcohol and water in film recovery assembly 15 through the 3rd stepping processes in film recovery assembly, reclaims and obtains alcohol by-products 8;
5th step, sends into the 2# methanol distillation column 14 tower reactor solution in ester recovery tower 16 through the 3rd step, reclaims the Ester 9 obtaining methyl glycolate, at ester recovery tower 16 overhead extraction waste water in the tower reactor of ester recovery tower 16; Described ester recovery tower 16 is totally 25 ~ 45 pieces of theoretical stages, and working pressure is 80kPa ~ 120kPa, and the liquid feeding position of ester recovery tower 16 is the medium position place of whole ester recovery tower 16, and still temperature is 120 ~ 155 DEG C.
The idiographic flow (see Fig. 1) of the byproduct recovery process of synthetic gas preparing ethylene glycol of the present invention is:
The thick product 1 of the ethylene glycol of being come by synthesizing section enters the middle part of 1# methanol distillation column 11, at the overhead vapours of 1# methanol distillation column 11 after condenser 20 condensation, condenser 3 is not directly discharged, phlegma enters return tank 19 and enters in 1# methanol distillation column 11 by pump reflux, and 1# methanol distillation column 11 side line reclaims byproduct methyl alcohol 2; The tower reactor solution part of 1# methanol distillation column 11 enter reboiler heat vaporized after return the tower reactor of 1# methanol distillation column 11, another part sends into the middle and upper part of de-ester tower 12 by pump 17; De-ester tower 12 overhead vapours is after condenser condenses, phlegma enters return tank and vacuumizes, part phlegma refluxes into de-ester tower 12 top, another part extraction fusel, water and Ester 22, and this fusel, water and Ester 22 sends into 2# methanol distillation column; 2# methanol distillation column 14 overhead vapours refluxes through condenser condenses rear section into 2# Methanol Recovery column overhead, the byproduct of extraction simultaneously methyl alcohol 2, the mixture 7 of 2# methanol distillation column 14 side take-off second alcohol and water, the mixture 7 of this second alcohol and water reclaims assembly 15 through film and reclaims alcohol by-products 8; The tower reactor solution part of 2# methanol distillation column 14 enter reboiler heat vaporized after return the tower reactor of 2# methanol distillation column 14, another part tower reactor solution is by being pumped in the middle part of ester recovery tower 16; An ester recovery tower 16 tower reactor solution part enter reboiler heat vaporized after return the tower reactor of ester recovery tower 16, namely another part extraction reclaims Esters such as obtaining methyl glycolate 9, the tower top of ester recovery tower 16 is after condenser condenses, partial reflux, extraction simultaneously and waste water 10 (if this waste water reaches wastewater discharge standard, directly can discharge, need if below standard to carry out waste water reclamation); A tower reactor solution part for de-ester tower 12 is sent into the middle and upper part of product tower 13 by pump 17, another part returns de-ester tower 12 tower reactor after being pumped into reboiler and being heat vaporized; The overhead vapours of product tower 13 is after condenser condenses, phlegma enters return tank and vacuumizes, part backflow enters the tower top of product tower 13, another part extraction that is 1, the azeotrope 5 of 2-butyleneglycol and ethylene glycol, product tower 13 side take-off obtains product premium grads ethylene glycol 4 (this premium grads ethylene glycol is the major product of the thick product of ethylene glycol) after condenser condenses, a product tower 13 tower reactor solution part through be pumped into reboiler heat vaporized after return the tower reactor of product tower 13, another part is directly through pump 17 extraction heavy constituent 6, and this heavy constituent is discharged as waste liquid.
Essential substance in the present invention in the thick product of the ethylene glycol of synthetic gas preparing ethylene glycol is ethylene glycol, methyl alcohol, ethanol, methyl glycolate, water, methylcarbonate etc.Recovery process equipment used of the present invention, on the basis of the equipment used of existing ethylene glycol purifying technique, the byproduct increased in the thick product of 1# methanol distillation column 11,2# methanol distillation column 14, film recovery assembly 15 and ester recovery tower 16 pairs of synthetic gas preparing ethylene glycols is further recycled, improve the utilization ratio of raw material, reduce Financial cost, reduce discharge of wastewater.
Embodiment 1
In the present embodiment, the concrete steps of the byproduct recovery process of synthetic gas preparing ethylene glycol are:
The first step, in the thick product 1 of ethylene glycol of synthetic gas preparing ethylene glycol, the mass percent of ethylene glycol is 45%, the mass percent 51% of methyl alcohol, the mass percent 0.5% of ethanol, the mass percent 1% of water, methyl glycolate 0.5%, impurity 2%, the thick product 1 of this ethylene glycol enters in the middle part of 1# methanol distillation column 11, the a small amount of non-condensable gas 3 of 1# methanol distillation column 11 tower top extraction after condensation, byproduct methyl alcohol 2 is reclaimed at 1# methanol distillation column 11 side line, this step reclaims the byproduct methyl alcohol (this purity refers to the massfraction of the middle methyl alcohol reclaiming the methanol solution obtained) that the purity obtained is more than or equal to 99.5%, the byproduct methyl alcohol reclaimed can prepare methyl nitrite as raw material for synthesizing section, the tower reactor solution of 1# methanol distillation column 11 sends into de-ester tower 12 middle and upper part,
Second step, introduce the tower reactor solution of the first step 1# methanol distillation column 11 in de-ester tower 12 middle and upper part after, de-ester tower 12 overhead vapours refluxes after condensation, and extraction fusel, water and Ester 22, this fusel, water and Ester 22 sends into the middle part of 2# methanol distillation column 14;
3rd step, enter the tower top solution of the de-ester tower 12 at the middle part of 2# methanol distillation column 14, be more than or equal to the byproduct methyl alcohol of 99.5% in the overhead extraction purity of 2# methanol distillation column 14, this byproduct methyl alcohol prepares methyl nitrite reuse as raw material for synthesizing section; The mixture 7 of 2# methanol distillation column 14 side take-off second alcohol and water, and the mixture 7 of this second alcohol and water is sent into film recovery assembly 15; The tower reactor solution of 2# methanol distillation column 14 sends into ester recovery tower 16;
4th step, the mixture 7 entering the second alcohol and water in film recovery assembly 15 through the 3rd stepping processes in film recovery assembly, reclaims and obtains alcohol by-products 8;
5th step, sends into the 2# methanol distillation column 14 tower reactor solution in ester recovery tower 16 through the 3rd step, reclaims the Ester 9 obtaining methyl glycolate, at ester recovery tower 16 overhead extraction waste water in the tower reactor of ester recovery tower 16.
In the present embodiment, the diameter of 1# methanol distillation column 11 is 90mm, totally 40 pieces of theoretical stages, decompression operation, and liquid feeding position is at the 23rd piece of theoretical stage, and R=1.8, liquid feeding temperature 65 DEG C, tower top temperature is 51 DEG C, and bottom temperature is 119 DEG C, reflux temperature 58 DEG C.The rate of recovery of 1# methanol distillation column side take-off byproduct methyl alcohol is: 1# methanol distillation column reclaims quality=95.68% of methyl alcohol in the thick product of quality/ethylene glycol of methyl alcohol.
De-ester tower 12 diameter is 110mm, and totally 40 pieces of theoretical stages, decompression operation, liquid feeding position is at the 10th piece of theoretical stage, and reflux ratio R=6, liquid feeding temperature 119 DEG C, tower top temperature is 36.6 DEG C, and bottom temperature is 155 DEG C, reflux temperature 48 DEG C.Take off the overhead extraction fusel of ester tower 12, water and Ester and enter 2# methanol distillation column;
The diameter of 2# methanol distillation column 14 is 40mm, totally 40 pieces of theoretical stages, atmospheric operation, liquid feeding position is at the 20th piece of theoretical stage, the position of side take-off (side is adopted) is the 30th piece of theoretical stage, reflux ratio R=5, liquid feeding temperature 36.6 DEG C, tower top temperature is 64.5 DEG C, bottom temperature is 96 DEG C, reflux temperature 64.5 DEG C, the byproduct methyl alcohol 2 of overhead extraction massfraction more than 99.5%, in the rate of recovery of 2# methanol distillation column byproduct methyl alcohol is: 2# methanol distillation column reclaims quality=4.15% of methyl alcohol in the thick product of quality/ethylene glycol of methyl alcohol; Reclaimed by 1# methanol distillation column 11 and 2# methanol distillation column 14 and obtain byproduct methyl alcohol, in the present embodiment, quality=99.83% of methyl alcohol in the rate of recovery=(quality+2# methanol distillation column that 1# methanol distillation column reclaims methyl alcohol reclaims the quality of methyl alcohol) thick product of/ethylene glycol of byproduct methyl alcohol.
The diameter of product tower 13 is 400mm, totally 160 pieces of theoretical stages, decompression operation, liquid feeding position is at the 45th piece of theoretical stage, side take-off position is the 131st piece of theoretical stage, liquid feeding temperature 155 DEG C, tower top temperature is 155 DEG C, bottom temperature is 160 DEG C, side take-off premium grads ethylene glycol 4 product (this product is the major product of synthetic gas preparing ethylene glycol), tower reactor extraction heavy constituent 6 (this heavy constituent is discharged as waste liquid), the azeotrope 5 of overhead extraction 1,2-butyleneglycol and ethylene glycol.
Ester recovery tower 16 diameter is 40mm, totally 30 pieces of theoretical stages, atmospheric operation, liquid feeding position at the 15th piece of theoretical stage, reflux ratio R=5, liquid feeding temperature is 96 DEG C, tower top temperature is 95 DEG C, bottom temperature is 153 DEG C, and reflux temperature 99.6 DEG C, the Esters 9 such as the methyl glycolate of methyl glycolate are rich in tower reactor extraction.Reclaimed by ester recovery tower 16 and obtain the Esters such as methyl glycolate 9, in the Esters 9 such as this methyl glycolate, the content of methyl glycolate is 89.25%, and the final rate of recovery obtaining alcohol by-products acid methyl esters that reclaims is: the rate of recovery=ester recovery tower of methyl glycolate reclaims quality=80% of methyl glycolate in the thick product of quality/ethylene glycol of methyl glycolate.
Reclaim assembly 15 recovery by film and obtain alcohol by-products 8; The rate of recovery=the film of alcohol by-products reclaims quality=68.8% that assembly reclaims ethanol in the thick product of quality/ethylene glycol of ethanol.
Embodiment 2
The recovery process process of the present embodiment is with embodiment 1, and the content of each component of the thick product of ethylene glycol 1 is with embodiment 1, and difference is that in the present embodiment, the design parameter of each tower is different,
In the present embodiment, 1# methanol distillation column 11 diameter is 60mm, totally 40 pieces of theoretical stages, decompression operation, liquid feeding position at the 23rd piece of theoretical stage, reflux ratio R=2, liquid feeding temperature 65 DEG C, tower top temperature is 50 DEG C, and bottom temperature is 67.8 DEG C, reflux temperature 59.5 DEG C.The rate of recovery of 1# methanol distillation column 11 side take-off byproduct methyl alcohol is: 1# methanol distillation column reclaims quality=39% of methyl alcohol in the thick product of quality/ethylene glycol of methyl alcohol.
The diameter of de-ester tower 12 is 250mm, and totally 40 pieces of theoretical stages, decompression operation, liquid feeding position is at the 10th piece of theoretical stage, and reflux ratio R=6, liquid feeding temperature 67.8 DEG C, tower top temperature is 29.4 DEG C, and bottom temperature is 155.4 DEG C, reflux temperature 40 DEG C.
The diameter of product tower 13 is 360mm, totally 180 pieces of theoretical stages, decompression operation, liquid feeding position is at the 50th piece of theoretical stage, side take-off position is 147 pieces of theoretical stages, liquid feeding temperature 155.4 DEG C, tower top temperature is 155 DEG C, and bottom temperature is 160.6 DEG C, side take-off premium grads ethylene glycol product, tower reactor extraction heavy constituent, the azeotrope of overhead extraction 1,2-butyleneglycol and ethylene glycol.
The diameter of 2# methanol distillation column 14 is 160mm, totally 40 pieces of theoretical stages, atmospheric operation, liquid feeding position is at the 20th piece of theoretical stage, side take-off position is the 30th piece of theoretical stage, reflux ratio R=6, liquid feeding temperature 29.4 DEG C, tower top temperature is 64.5 DEG C, bottom temperature is 98.9 DEG C, reflux temperature 64.5 DEG C, overhead extraction massfraction is the byproduct methyl alcohol of more than 99.5%, in the rate of recovery of 2# methanol distillation column byproduct methyl alcohol is: 2# methanol distillation column reclaims quality=60.78% of methyl alcohol in the thick product of quality/ethylene glycol of methyl alcohol; Reclaimed by 1# methanol distillation column 11 and 2# methanol distillation column 14 and obtain byproduct methyl alcohol, in the present embodiment, quality=99.78% of methyl alcohol in the rate of recovery=(quality+2# methanol distillation column that 1# methanol distillation column reclaims methyl alcohol reclaims the quality of methyl alcohol) thick product of/ethylene glycol of byproduct methyl alcohol.
The diameter of ester recovery tower 16 is 40mm, totally 30 pieces of theoretical stages, atmospheric operation, liquid feeding position is at 15 pieces of theoretical stages, reflux ratio R=5, liquid feeding temperature 98.9 DEG C, tower top temperature is 95.3 DEG C, bottom temperature is 144 DEG C, reflux temperature 99.6 DEG C, the Esters 9 such as the methyl glycolate of methyl glycolate are rich in tower reactor extraction, wherein the content of methyl glycolate is 80%, the rate of recovery that final recovery obtains alcohol by-products acid methyl esters is: the rate of recovery=ester recovery tower of methyl glycolate reclaims quality=99.2% of methyl glycolate in the thick product of quality/ethylene glycol of methyl glycolate.
Reclaim assembly 15 recovery by film and obtain alcohol by-products 8; The rate of recovery=the film of alcohol by-products reclaims quality=73.4% that assembly reclaims ethanol in the thick product of quality/ethylene glycol of ethanol.
Embodiment 3
The recovery process process of the present embodiment is with embodiment 1, difference is that in the present embodiment, the design parameter of each tower is different, the mass percent that the content of each main ingredient of the thick product of ethylene glycol 1 is respectively ethylene glycol is 56%, the mass percent of methyl alcohol is 40%, the mass percent 0.5% of ethanol, the mass percent 1% of water, methyl glycolate 0.5%, impurity 2%.
In the present embodiment, 1# methanol distillation column 11 diameter is 80mm, totally 40 pieces of theoretical stages, atmospheric operation, and liquid feeding position is at the 25th piece of theoretical stage, and reflux ratio R=2, liquid feeding temperature 65 DEG C, tower top temperature is 56 DEG C, and bottom temperature is 90 DEG C, reflux temperature 60 DEG C.The rate of recovery of 1# methanol distillation column 11 side take-off byproduct methyl alcohol is: 1# methanol distillation column reclaims quality=74.65% of methyl alcohol in the thick product of quality/ethylene glycol of methyl alcohol.
The diameter of de-ester tower 12 is 160mm, and totally 40 pieces of theoretical stages, decompression operation, liquid feeding position is at the 10th piece of theoretical stage, and reflux ratio R=6, liquid feeding temperature 90 DEG C, tower top temperature is 32 DEG C, and bottom temperature is 155 DEG C, reflux temperature 52.5 DEG C.
The diameter of product tower 13 is 400mm, totally 160 pieces of theoretical stages, decompression operation, liquid feeding position is at the 45th piece of theoretical stage, side take-off position is 131 pieces of theoretical stages, liquid feeding temperature 155 DEG C, tower top temperature is 155 DEG C, and bottom temperature is 160 DEG C, side take-off premium grads ethylene glycol product, tower reactor extraction heavy constituent, the azeotrope of overhead extraction 1,2-butyleneglycol and ethylene glycol.
The diameter of 2# methanol distillation column 14 is 90mm, totally 40 pieces of theoretical stages, atmospheric operation, liquid feeding position is at the 20th piece of theoretical stage, side take-off position is the 30th piece of theoretical stage, reflux ratio R=6, liquid feeding temperature 32 DEG C, tower top temperature is 64.5 DEG C, bottom temperature is 98.6 DEG C, reflux temperature 64.5 DEG C, overhead extraction massfraction is the byproduct methyl alcohol of more than 99.5%, in the rate of recovery of 2# methanol distillation column byproduct methyl alcohol is: 2# methanol distillation column reclaims quality=25.2% of methyl alcohol in the thick product of quality/ethylene glycol of methyl alcohol; Reclaimed by 1# methanol distillation column 11 and 2# methanol distillation column 14 and obtain byproduct methyl alcohol, in the present embodiment, quality=99.85% of methyl alcohol in the rate of recovery=(quality+2# methanol distillation column that 1# methanol distillation column reclaims methyl alcohol reclaims the quality of methyl alcohol) thick product of/ethylene glycol of byproduct methyl alcohol.
The diameter of ester recovery tower 16 is 40mm, totally 30 pieces of theoretical stages, atmospheric operation, liquid feeding position is at 15 pieces of theoretical stages, reflux ratio R=5, liquid feeding temperature 98.6 DEG C, tower top temperature is 95 DEG C, bottom temperature is 137 DEG C, reflux temperature 95 DEG C, the Esters 9 such as the methyl glycolate of methyl glycolate are rich in tower reactor extraction, in the Esters such as methyl glycolate 9, the content of methyl glycolate is 82.44%, the rate of recovery that final recovery obtains alcohol by-products acid methyl esters is: the rate of recovery=ester recovery tower of methyl glycolate reclaims quality=98.8% of methyl glycolate in the thick product of quality/ethylene glycol of methyl glycolate.
Reclaim assembly 15 recovery by film and obtain alcohol by-products 8; The rate of recovery=the film of alcohol by-products reclaims quality=72.9% that assembly reclaims ethanol in the thick product of quality/ethylene glycol of ethanol.
Embodiment 4
The recovery process process of the present embodiment is with embodiment 1, difference is that in the present embodiment, the design parameter of each tower is different, the mass percent that the content of each main ingredient of the thick product of ethylene glycol 1 is respectively ethylene glycol is 31%, the mass percent 65% of methyl alcohol, the mass percent 0.5% of ethanol, the mass percent 1% of water, methyl glycolate 0.5%, impurity 2%.
In the present embodiment, 1# methanol distillation column 11 diameter is 85mm, totally 40 pieces of theoretical stages, atmospheric operation, liquid feeding position at the 23rd piece of theoretical stage, reflux ratio R=1.8, liquid feeding temperature 65 DEG C, tower top temperature is 57 DEG C, and bottom temperature is 72.5 DEG C, reflux temperature 64.5 DEG C.The rate of recovery of 1# methanol distillation column 11 side take-off byproduct methyl alcohol is: 1# methanol distillation column reclaims quality=75.07% of methyl alcohol in the thick product of quality/ethylene glycol of methyl alcohol.
The diameter of de-ester tower 12 is 190mm, and totally 40 pieces of theoretical stages, decompression operation, liquid feeding position is at the 10th piece of theoretical stage, and reflux ratio R=6, liquid feeding temperature 72.5 DEG C, tower top temperature is 30 DEG C, and bottom temperature is 155.4 DEG C, reflux temperature 55 DEG C.
The diameter of product tower 13 is 345mm, totally 180 pieces of theoretical stages, decompression operation, liquid feeding position is at the 50th piece of theoretical stage, side take-off position is 147 pieces of theoretical stages, liquid feeding temperature 155.4 DEG C, tower top temperature is 155 DEG C, and bottom temperature is 160.6 DEG C, side take-off premium grads ethylene glycol product, tower reactor extraction heavy constituent, the azeotrope of overhead extraction 1,2-butyleneglycol and ethylene glycol.
The diameter of 2# methanol distillation column 14 is 100mm, totally 40 pieces of theoretical stages, atmospheric operation, liquid feeding position is at the 20th piece of theoretical stage, side take-off position is the 30th piece of theoretical stage, reflux ratio R=5, liquid feeding temperature 30 DEG C, tower top temperature is 64.5 DEG C, bottom temperature is 99 DEG C, reflux temperature 64.5 DEG C, overhead extraction massfraction is the byproduct methyl alcohol of more than 99.5%, in the rate of recovery of 2# methanol distillation column byproduct methyl alcohol is: 2# methanol distillation column reclaims quality=24.76% of methyl alcohol in the thick product of quality/ethylene glycol of methyl alcohol; Reclaimed by 1# methanol distillation column 11 and 2# methanol distillation column 14 and obtain byproduct methyl alcohol, in the present embodiment, quality=99.83% of methyl alcohol in the rate of recovery=(quality+2# methanol distillation column that 1# methanol distillation column reclaims methyl alcohol reclaims the quality of methyl alcohol) thick product of/ethylene glycol of byproduct methyl alcohol.
The diameter of ester recovery tower 16 is 40mm, totally 30 pieces of theoretical stages, atmospheric operation, liquid feeding position is at the 15th piece of theoretical stage, reflux ratio R=5, liquid feeding temperature 97.6 DEG C, tower top temperature is 93.9 DEG C, bottom temperature is 126.3 DEG C, reflux temperature 95 DEG C, the Esters 9 such as the methyl glycolate of methyl glycolate are rich in tower reactor extraction, in the Esters 9 such as this methyl glycolate, the content of methyl glycolate is 75%, the rate of recovery that final recovery obtains alcohol by-products acid methyl esters is: the rate of recovery=ester recovery tower of methyl glycolate reclaims quality=95.6% of methyl glycolate in the thick product of quality/ethylene glycol of methyl glycolate.
Reclaim assembly 15 recovery by film and obtain alcohol by-products 8; The rate of recovery=the film of alcohol by-products reclaims quality=67.2% that assembly reclaims ethanol in the thick product of quality/ethylene glycol of ethanol.
Find out from above-mentioned four embodiments, the present invention can reclaim exhausted large most byproduct methyl alcohol (byproduct Methanol Recovery rate is about more than 99.7%) in the thick product of ethylene glycol that synthetic gas preparing ethylene glycol obtains, the purity of the byproduct methyl alcohol of this recovery is higher, all more than 99.5%, this byproduct methyl alcohol can continue to prepare methyl nitrite as raw material for synthesizing section.The methyl glycolate (rate of recovery of methyl glycolate is more than 80%) of energy recovery part alcohol by-products (rate of recovery of alcohol by-products is about more than 67.2%) of the present invention and part simultaneously.Can making full use of raw material be realized by the design of recovery process of the present invention, effectively save investment of production, further reduced environmental pollution simultaneously, be more conducive to industrial applications.
The present invention does not address part and is applicable to prior art.
Claims (1)
1. a byproduct recovery process for synthetic gas preparing ethylene glycol, is characterized in that the concrete steps of this recovery process are:
The first step, in the middle part of the ethylene glycol thick product introduction 1# methanol distillation column of synthetic gas preparing ethylene glycol, 1# Methanol Recovery column overhead extraction non-condensable gas after condensation, byproduct methyl alcohol is reclaimed at 1# methanol distillation column side line, this step reclaims the byproduct methyl alcohol that the purity obtained is more than or equal to 99.5%, and the byproduct methyl alcohol of recovery can as raw material for synthesizing section; The tower reactor solution of 1# methanol distillation column sends into de-ester tower middle and upper part; Described 1# methanol distillation column is totally 20 ~ 55 pieces of theoretical stages, and working pressure is 80kPa ~ 120kPa, and the position that side is adopted is 4th ~ 6 pieces of theoretical stages, and still temperature is 60 ~ 130 DEG C;
Second step, introduce the tower reactor solution of the first step 1# methanol distillation column in de-ester tower middle and upper part after, de-ester column overhead steam refluxes after condensation, and extraction fusel, water and Ester, this fusel, water and Ester send into the middle part of 2# methanol distillation column; Described de-ester tower totally 35 ~ 55 pieces of theoretical stages, working pressure is 10kPa ~ 20kPa, and de-ester tower liquid feeding position is the position, middle and upper part of whole de-ester tower, and still temperature is 140 ~ 165 DEG C;
3rd step, enters the tower top solution of the de-ester tower at the middle part of 2# methanol distillation column, is more than or equal to the byproduct methyl alcohol of 99.5% in the overhead extraction purity of 2# methanol distillation column, and this byproduct methyl alcohol supplies synthesizing section reuse as raw material; The mixture of 2# methanol distillation column side take-off second alcohol and water, the mixture of this second alcohol and water enters film and reclaims assembly; The tower reactor solution of 2# methanol distillation column sends into ester recovery tower; Described 2# methanol distillation column is totally 35 ~ 55 pieces of theoretical stages, the medium position place of working pressure to be the liquid feeding position of 80kPa ~ 120kPa, 2# methanol distillation column be whole 2# methanol distillation column, and still temperature is 80 ~ 105 DEG C;
4th step, the mixture entering the second alcohol and water in film recovery assembly through the 3rd stepping processes in film recovery assembly, reclaims and obtains alcohol by-products;
5th step, sends into the 2# methanol distillation column tower reactor solution in ester recovery tower through the 3rd step, reclaims the Ester obtaining methyl glycolate, at ester recovery tower overhead extraction waste water in the tower reactor of ester recovery tower; Described ester recovery tower is totally 25 ~ 45 pieces of theoretical stages, and working pressure is 80kPa ~ 120kPa, and the liquid feeding position of ester recovery tower is the medium position place of whole ester recovery tower, and still temperature is 120 ~ 155 DEG C.
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| CN114543576A (en) * | 2022-01-25 | 2022-05-27 | 中建石化工程有限公司 | System and method for utilizing waste heat of byproduct steam of coal-to-ethylene glycol device |
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