CN204211669U - Commercial syngas pressure carbonylation produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol - Google Patents

Commercial syngas pressure carbonylation produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol Download PDF

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CN204211669U
CN204211669U CN201420408878.4U CN201420408878U CN204211669U CN 204211669 U CN204211669 U CN 204211669U CN 201420408878 U CN201420408878 U CN 201420408878U CN 204211669 U CN204211669 U CN 204211669U
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outlet
pipeline
tower
feed
mouth
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王保明
王东辉
李玉江
徐长青
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SHANGHAI WUZHENG ENGINEERING Co Ltd
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SHANGHAI WUZHENG ENGINEERING Co Ltd
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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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/04—Preparation of esters of nitrous acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The utility model relates to a kind of commercial syngas pressure carbonylation and produces dimethyl oxalate the apparatus system of Hydrogenation ethylene glycol, comprises esterification system, oxonation system, periodic off-gases and to be coupled with spent acid recovery system and hydrogenation reaction system; Esterification system response generates methyl nitrite, methyl nitrite generates the carbonyl compounds being mainly dimethyl oxalate and methylcarbonate through oxonation system, carbonyl compounds obtains methylcarbonate product after being separated, and residue dimethyl oxalate is through hydrogenation reaction system generating glycol product; And the spent acid of esterification and the periodic off-gases of oxonation recycle recycle through the periodic off-gases recovery system that to be coupled with spent acid; This apparatus system has the feature of remarkable energy efficient, and connected applications useful matter circulation step, particularly nitric acid waste recycle and periodic off-gases recycle are highly coupled and are separated the recycle and reuse with hydrogen in reactor off-gas, Be very effective.

Description

Commercial syngas pressure carbonylation produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol
Technical field
The utility model relates to a kind of apparatus system of commercial syngas preparing ethylene glycol, particularly relates to a kind of commercial syngas pressure carbonylation and produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol.
Background technology
Ethylene glycol is a kind of broad-spectrum chemical, be mainly used in the multiple production fields such as trevira (PET), frostproofer, thanomin and explosive, and be widely used as solvent, lubricant and softening agent, and ethylene glycol in the application of PET PET industry close to 95%.In current industrial, ethylene glycol is produced the main oil ethene that adopts and is obtained oxyethane through gaseous oxidation, then through the route of liquid-phase catalysis hydration preparing ethylene glycol.But along with international oil price occupies high price for a long time in recent years, the current world is that waste ethylene glycol industrial chain faces immense pressure with ethene.Therefore, adopt synthetic gas preparing ethylene glycol technological line due to low production cost, more and more cause and pay close attention to widely.
Mainly adopt shell and tube reactor in current coal-ethylene glycol technological process, it is low that ubiquity heat of reaction moves thermo-efficiency, and utilization coefficient and the packing factor of catalyzer are low, thus affect reactor throughput.
Patent (publication number CN101462961) provides a kind of technique of producing ethylene glycol with coproduction product dimethyl carbonate, technological process comprises CO and methyl nitrite synthesizing dimethyl oxalate and methylcarbonate process, fractionation by distillation obtains methylcarbonate product process, heavy constituent dimethyl oxalate shortening synthesizing glycol process, also comprises the regenerative response process of methyl nitrite in system.But reactor adopts shell and tube reactor, the waste gas produced in reaction process and waste liquid do not realize circulation and stress recycling, and plant energy consumption is higher, can not meet the environmental protection needs that country is growing.
Patent (publication number CN101830806) discloses the method and apparatus of a kind of co-producing dimethyl carbonate and dimethyl oxalate, patent adopts two oxonation devices, first is dimethyl carbonate synthesis reactor, second is the reactor of dimethyl oxalate, enter two reactors respectively after methyl nitrite reaction generates and produce methylcarbonate and dimethyl oxalate respectively, then product carries out separating-purifying, this is from Process Route angle, its essence is only the simple cumulative of two class reactors, really cannot realize the practical significance of DMO coproduction DMC in same device.Also do not carry out energy-optimised to integrated artistic flow process in patent, also do not have announcement to environmental practice necessary in reaction process.Experimentation is not also course of industrialization.
In addition, the nitric acid by product produced in the loss of speeding to let slip NO in journey and processing reaction process is a stubborn problem.Patent CN201210531022.1 discloses a kind of method, is concentrated by the nitric acid of generation, then reacts with it with the circulation gas of part containing NO, produces NO 2, supplement and get back to methyl nitrite regeneration reactor.But also contain the gas such as a large amount of methyl nitrite and methyl alcohol containing in the circulation gas of NO, these gases also can react with concentrated nitric acid, and product is more complicated, thus affect device usefulness.
In sum, current coal-ethylene glycol technique mainly exists that catalyst utilization is low, catalyst loading coefficient is low, and in device, valuable gas can not make full use of, on the contrary contaminate environment, apparatus system heat can not fully be utilized, thus causes Social and economic benef@undesirable.
Summary of the invention
The purpose of this utility model is that the raw material availability solving the existence of current production ethylene glycol technology is low, production cost is high, catalyst utilization is low, packing factor is low, facility investment is excessive, single series equipment cannot maximize by adaptive device, high and the device of system consumption uses and can not meet country day by day to problems such as the requirements of industrial environment, provide a kind of for improving single series plant capacity, treating tail gas, by-product reclaim and the technique of raw material comprehensive utilization and apparatus system thereof.
The utility model is achieved through the following technical solutions:
Commercial syngas pressure carbonylation produces dimethyl oxalate an apparatus system for Hydrogenation ethylene glycol, comprises oxonation system, esterification system, periodic off-gases and to be coupled with spent acid recovery system and hydrogenation reaction system;
Described oxonation system comprises oxonation device, the first gas-liquid separator, Methanol Wash Column, methanol rectifying tower and DMO rectifying tower; Described oxonation device is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described first gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described Methanol Wash Column is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described methanol rectifying tower is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described DMO rectifying tower is provided with underfeed mouth, top exit and outlet at bottom;
Described esterification system comprises esterification reaction tower and methanol distillation column; Described esterification reaction tower is provided with its top feed mouth, upper feed inlet, multiple underfeed mouth, middle part reflux inlet, top exit and outlet at bottom; Described methanol distillation column is provided with middle and lower part opening for feed, underfeed mouth, top exit and outlet at bottom;
The described periodic off-gases recovery system that is coupled with spent acid comprises nitric acid concentration tower, NO recovery tower, MN recovery tower and pressure-variable adsorption tank; Described nitric acid concentration tower is provided with middle part opening for feed, top exit and outlet at bottom; Described NO recovery tower is provided with its top feed mouth, middle part opening for feed, bottom feed mouth, top exit and outlet at bottom; Described MN recovery tower is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described pressure-variable adsorption tank is provided with opening for feed, reclaims gas outlet and row's bleeder holes;
Described hydrogenation reaction system comprises and adds Recycle hydrogen compressor, hydrogenator, the second gas-liquid separator, membrane separation apparatus, method separation tower, light constituent rectifying tower and ethylene glycol product tower; The described Recycle hydrogen compressor that adds comprises import and outlet; Described hydrogenator is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described second gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described membrane separation apparatus is provided with opening for feed, reclaims gas outlet and row's bleeder holes; Described method separation tower is provided with middle part opening for feed, the outlet of top non-condensable gas, top liquid phase light fraction outlet and the outlet of bottom liquid phases heavy constituent; Described light constituent rectifying tower is provided with underfeed mouth, top exit and outlet at bottom; Described ethylene glycol product tower is provided with underfeed mouth, top exit, upper outlet and outlet at bottom;
Its top feed mouth of described oxonation device and CO feed conduit and N 2feed conduit connects through pipeline; The bottom discharge mouth of described oxonation device is connected through pipeline with the opening for feed of described first gas-liquid separator; The pneumatic outlet of described first gas-liquid separator is connected through pipeline with the underfeed mouth of described Methanol Wash Column; The liquid exit of described first gas-liquid separator is connected through pipeline with the upper feed inlet of described methanol rectifying tower; The top exit of described Methanol Wash Column is provided with branch outlet A and branch outlet B, and branch outlet A is connected through pipeline with a underfeed mouth of described esterification reaction tower, and branch outlet B is connected through pipeline with the bottom feed mouth of described NO recovery tower; The outlet at bottom of described Methanol Wash Column is connected through pipeline with the underfeed mouth of described methanol rectifying tower; The top exit of described methanol rectifying tower is connected through pipeline with the upper feed inlet of described esterification reaction tower; The outlet at bottom of described methanol rectifying tower is connected through pipeline with the underfeed mouth of described DMO rectifying tower; The outlet at bottom of described DMO rectifying tower is connected through pipeline with its top feed mouth of described hydrogenator, and the top exit of described DMO rectifying tower is DMC products export;
Other underfeed mouth of described esterification reaction tower and NO feed conduit and multichannel O 2feed conduit connects through pipeline respectively; Its top feed mouth of described esterification reaction tower is connected through pipeline with methanol feedstock pipeline; The outlet at bottom of described esterification reaction tower is provided with branch outlet C and branch outlet D, and branch outlet C is connected through pipeline with the middle part reflux inlet of described esterification reaction tower, and branch outlet D is connected through pipeline with the underfeed mouth of described methanol distillation column; The top exit of described esterification reaction tower is connected through pipeline with its top feed mouth of described oxonation device; The top exit of described methanol distillation column is provided with branch outlet E and branch outlet F, and branch outlet E is connected through pipeline with the upper feed inlet of described esterification reaction tower, and branch outlet F is connected through pipeline with the upper feed inlet of described MN recovery tower; The outlet at bottom of described methanol distillation column is connected through pipeline with the middle part opening for feed of described nitric acid concentration tower;
The top exit of described nitric acid concentration tower is waste liquid relief outlet; The outlet at bottom of described nitric acid concentration tower is connected through pipeline with the middle part opening for feed of described NO recovery tower; The top exit of described NO recovery tower is connected through pipeline with the underfeed mouth of described MN recovery tower; The outlet at bottom of described NO recovery tower is connected through pipeline with the middle and lower part opening for feed of described methanol distillation column; The top exit of described MN recovery tower is connected through pipeline with the opening for feed of described pressure-variable adsorption tank; The outlet at bottom of described MN recovery tower is connected through pipeline with the upper feed inlet of described esterification reaction tower; The recovery gas outlet of described pressure-variable adsorption tank is connected through pipeline with its top feed mouth of described oxonation device; Row's bleeder holes of described pressure-variable adsorption tank is connected through pipeline with out-of-bounds retrieving arrangement;
The described import adding Recycle hydrogen compressor is connected through pipeline with plant hydrogen feed conduit, described in add Recycle hydrogen compressor its top feed mouth of outlet and described hydrogenator be connected through pipeline; The bottom discharge mouth of described hydrogenator is connected through pipeline with the opening for feed of described second gas-liquid separator; The pneumatic outlet of described second gas-liquid separator is provided with branch outlet G and branch outlet H, and branch outlet G is connected through pipeline with the described import adding Recycle hydrogen compressor, and branch outlet H is connected through pipeline with the opening for feed of described membrane separation apparatus; The liquid exit of described second gas-liquid separator is connected through pipeline with the underfeed mouth of described method separation tower; The top non-condensable gas outlet of described method separation tower is connected through pipeline with the opening for feed of described membrane separation apparatus; The top liquid phase light fraction outlet of described method separation tower is provided with branch outlet I and branch outlet J, and branch outlet I is connected through pipeline with the upper feed inlet of described Methanol Wash Column, and branch outlet J is connected through pipeline with its top feed mouth of described NO recovery tower; The bottom liquid phases heavy constituent outlet of described method separation tower is connected through pipeline with the underfeed mouth of described light constituent rectifying tower; The top light fraction outlet of described light constituent rectifying tower is connected through pipeline with out-of-bounds alcohol retrieving arrangement; The bottom heavy constituent outlet of described light constituent rectifying tower is connected through pipeline with the underfeed mouth of described ethylene glycol product tower; The top exit of described ethylene glycol product tower and out-of-bounds 1,2-BDO recycling and processing device connect through pipeline; The outlet at bottom of described ethylene glycol product tower is connected through pipeline with out-of-bounds recycling and processing device; The upper outlet of described ethylene glycol product tower is ethylene glycol product outlet; Row's bleeder holes of described membrane separation apparatus is connected through pipeline with out-of-bounds retrieving arrangement, and the recovery gas outlet of described membrane separation apparatus is connected through pipeline with its top feed mouth of described hydrogenator.
Described oxonation device is externally connected with dehydration tower; Described dehydration tower is provided with opening for feed and dry gas outlet; The top exit of described esterification reaction tower is connected through pipeline with the opening for feed of described dehydration tower with the recovery gas outlet of described pressure-variable adsorption tank; The dry gas outlet of described dehydration tower is connected through pipeline with described oxonation device its top feed mouth.
Described dehydration tower is made up of the mole sieve drier A of two alternate runs and regeneration and mole sieve drier B; Filled with adsorbent in mole sieve drier A and mole sieve drier B; Described sorbent material is selected from 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 9A molecular sieve and calcium oxide.
The bottom discharge mouth of described oxonation device is connected with outlet heat exchanger I; Described outlet heat exchanger I is provided with cold logistics import, cold stream outlet, thermal material import and hot stream outlet; Described CO feed conduit, N 2the dry gas outlet of feed conduit and dehydration tower is connected through pipeline with the cold logistics import of described outlet heat exchanger I; The cold stream outlet of described outlet heat exchanger I is connected through pipeline with its top feed mouth of described oxonation device; The bottom discharge mouth of described oxonation device is connected through pipeline with the hot logistics import of described outlet heat exchanger I; The hot stream outlet of described outlet heat exchanger I is connected through pipeline with the opening for feed of described first gas-liquid separator.
Described oxonation device is externally connected with drum I; Described drum I is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum I is connected through pipeline with refrigerant feed conduit; The refrigerant exit of described drum I is connected through pipeline with the bottom refrigerant import of described oxonation device; The top refrigerant exit of described oxonation device is connected through pipeline with the liquid-vapor mixture import of described drum I; The vapour outlet of described drum I is connected through pipeline with out-of-bounds vapor-recovery system.
Carbonylation recycle compressor is connected with between the branch outlet A of described Methanol Wash Column and the underfeed mouth of described esterification reaction tower; Described carbonylation recycle compressor is provided with import and outlet; Described branch outlet A is connected through pipeline with the import of described carbonylation recycle compressor; The outlet of described carbonylation recycle compressor is connected through pipeline with the underfeed mouth of described esterification reaction tower.
Compressor is connected with between the top exit of described NO recovery tower and the bottom feed mouth of described MN recovery tower; Described compressor is provided with import and outlet; The top exit of described NO recovery tower is connected through pipeline with the import of described compressor; The outlet of described compressor is connected through pipeline with the bottom feed mouth of described MN recovery tower.
The bottom discharge mouth of described hydrogenator is connected with outlet heat exchanger II; Described outlet heat exchanger II is provided with cold logistics import, cold stream outlet, thermal material import and hot stream outlet; The recovery gas outlet of the outlet at bottom of described DMO rectifying tower, described membrane separation apparatus and described in add Recycle hydrogen compressor the cold logistics import of outlet and described outlet heat exchanger II be connected through pipeline; The cold stream outlet of described outlet heat exchanger II is connected through pipeline with its top feed mouth of described hydrogenator; The bottom discharge mouth of described hydrogenator is connected through pipeline with the hot logistics import of described outlet heat exchanger II; The hot stream outlet of described outlet heat exchanger II is connected through pipeline with the opening for feed of described second gas-liquid separator.
Its top feed mouth of described hydrogenator is connected with the well heater that goes into operation; The described well heater that goes into operation is provided with opening for feed and discharge port; The cold stream outlet of described outlet heat exchanger II is connected through pipeline with the opening for feed of the described well heater that goes into operation; The discharge port of the described well heater that goes into operation is connected through pipeline with its top feed mouth of described hydrogenator.
Described hydrogenator is externally connected with drum II; Described drum II is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum II is connected through pipeline with refrigerant feed conduit; The refrigerant exit of described drum II is connected through pipeline with the bottom refrigerant import of described hydrogenator; The top refrigerant exit of described hydrogenator is connected through pipeline with the liquid-vapor mixture import of described drum II; The vapour outlet of described drum II is connected through pipeline with out-of-bounds vapor-recovery system.
Described second gas-liquid separator comprises high-pressure gas-liquid separator and low-pressure gas-liquid separator; Described high-pressure gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described low-pressure gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; The hot stream outlet of described outlet heat exchanger II is connected through pipeline with the opening for feed of described high-pressure gas-liquid separator; The pneumatic outlet of described high-pressure gas-liquid separator is provided with branch outlet K and branch outlet L, and branch outlet K is connected through pipeline with the described import adding Recycle hydrogen compressor, and branch outlet L is connected through pipeline with the opening for feed of described low-pressure gas-liquid separator; The liquid exit of described high-pressure gas-liquid separator is connected through pipeline with the middle part opening for feed of described method separation tower; The pneumatic outlet of described low-pressure gas-liquid separator is connected through pipeline with the opening for feed of described membrane separation apparatus; The liquid exit of described low-pressure gas-liquid separator is connected through pipeline with the middle part opening for feed of described method separation tower.
Methanol absorption tank is provided with before the opening for feed of described membrane separation apparatus; Described methanol absorption tank is provided with opening for feed and clean gas outlet; The pneumatic outlet of described low-pressure gas-liquid separator is connected through pipeline with the opening for feed of described methanol absorption tank with the top non-condensable gas outlet of described method separation tower; The clean gas outlet of described methanol absorption tank is connected through pipeline with the opening for feed of described membrane separation apparatus.
Preferably, described oxonation device is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
Preferably, described oxonation device is board-like fixed bed oxonation device.
Preferably, the center of described board-like fixed bed oxonation device is provided with plate groups lock chamber, and be provided with plate groups in described plate groups lock chamber, described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber to board-like fixed bed oxonation device inwall between be provided with beds; Be filled with oxonation catalyzer in beds, described beds is also provided with top entry and outlet at bottom; In the bottom of described board-like fixed bed oxonation device, the bottom refrigerant import of described board-like fixed bed oxonation device is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed oxonation device; At the top of described board-like fixed bed oxonation device, the its top feed mouth of described board-like fixed bed oxonation device is connected through pipeline with the top entry of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed oxonation device.
Preferably, described esterification reaction tower is packing tower.
Preferably, described esterification reaction tower is the column plate-filler mixing column simultaneously with deck portion and filler filling part.
Preferably, described Methanol Wash Column, methanol rectifying tower, methanol distillation column, NO recovery tower, MN recovery tower, DMO rectifying tower and nitric acid concentration tower are packing tower, tray column or bubble-plate column.
Preferably, the filler loaded in described packing tower is dumped packing or High Efficient Standard Packing; The shape of described dumped packing is the shape of a saddle, Raschig ring, Pall ring, wheel shape, rectangular saddle ring, spherical or column; Described High Efficient Standard Packing is ripple packing, grid packing or Impulse packing.
Preferably, described hydrogenator is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
Preferred, described hydrogenator is board-like fixed bed hydrogenation reactor.
Preferably, the center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, is provided with plate groups in described plate groups lock chamber, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber to board-like fixed bed hydrogenation reactor inwall between be provided with beds; Be filled with catalyst for hydrogenation in described beds, described beds is also provided with top entry and outlet at bottom; In the bottom of described board-like fixed bed hydrogenation reactor, the bottom refrigerant import of described board-like fixed bed hydrogenation reactor is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed hydrogenation reactor; At the top of described board-like fixed bed hydrogenation reactor, the its top feed mouth of described board-like fixed bed hydrogenation reactor is connected through pipeline with the top entry of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed hydrogenation reactor.
Preferably, described membrane separation apparatus is in parallel or be connected in series and form by 1 ~ 100 hollow fiber film assembly.
Commercial syngas pressure carbonylation produces dimethyl oxalate and a technique for Hydrogenation ethylene glycol, for adopting technical grade NO, O 2with methyl alcohol be raw material generation esterification generate methyl nitrite, then carry out oxonation with technical grade CO and methyl nitrite and generate the carbonyl compounds being mainly dimethyl oxalate and methylcarbonate, carbonyl compounds obtains methylcarbonate product after being separated, and dimethyl oxalate is through follow-up hydrogenation generating glycol product; And the spent acid of esterification and the periodic off-gases of oxonation are through coupling recycling recycle.
Reaction equation is as follows:
Esterification: 4NO+O 2+ 4CH 3oH → 4CH 3oNO+2H 2o;
Oxonation: 2CO+2CH 3oNO → (COOCH 3) 2+ 2NO;
Hydrogenation reaction: (COOCH 3) 2+ 4H 2→ (CH 2oH) 2+ 2CH 3oH;
Total reaction: 4CO+O 2+ 8H 2→ 2 (CH 2oH) 2+ 2H 2o;
Described a kind of commercial syngas pressure carbonylation produces dimethyl oxalate and the technique of Hydrogenation ethylene glycol, specifically comprises the following steps:
(1) in esterification reaction tower, technical grade NO, O is passed into 2esterification is carried out with methyl alcohol; Esterification column overhead methyl nitrite gas mixture passes into oxonation device and carries out oxonation; Esterification reaction tower tower reactor acidity alcohol solution is partly refluxed to esterification reaction tower, and part passes into methanol distillation column; The methanol fractions of methanol distillation column recovered overhead is circulated to esterification reaction tower recycle, and all the other enter MN recovery tower as washings; Methanol distillation column tower reactor spent acid enters nitric acid concentration tower and carries out concentration;
(2) from methyl nitrite and technical grade CO, N of esterification reaction tower 2charging enters oxonation device, under oxonation catalyzer exists, oxonation occurs; The temperature of oxonation is 30 ~ 200 DEG C, and reaction pressure is 1 ~ 10MPa, gas hourly space velocity 3000 ~ 30000h -1;
(3) carbonyl compounds enters the first gas-liquid separator generation gas-liquid separation, and gas phase enters Methanol Wash Column, and liquid phase enters methanol rectifying tower; Methanol Wash Column top gaseous phase component Parts is circulated to esterification reaction tower, and part enters NO recovery tower as periodic off-gases and recycles; Methanol Wash Column tower bottoms phase component enters methanol rectifying tower and carries out rectifying separation; The methyl alcohol of methanol rectifying tower recovered overhead and methyl nitrite mixture are circulated to esterification reaction tower recycling, and tower reactor heavy constituent enters DMO rectifying tower; DMO rectifying tower tower top obtains DMC product, and tower reactor dimethyl oxalate component then enters hydrogenator and carries out hydrogenation reaction;
(4) from the spent acid of methanol distillation column after nitric acid concentration tower concentrate to concentration of nitric acid is 10 ~ 68wt%, be circulated to NO recovery tower; In NO recovery tower, concentrated nitric acid, methyl alcohol and the periodic off-gases generation esterification regenerative response from Methanol Wash Column; NO recovery tower top gaseous phase light constituent enters MN recovery tower, and the nitric acid waste containing methyl alcohol that tower reactor produces is circulated to methanol distillation column and recycles further; In MN recovery tower, gas-phase feed, after reclaiming methanol wash, enters pressure-variable adsorption tank, and MN recovery tower tower reactor enters esterification reaction tower containing the alcoholic solution circulation of methyl nitrite; The isolated CO of pressure-variable adsorption tank 2be disposed to and out-of-bounds process, the N of recovery 2the recycle of oxonation device is entered with CO purified gas;
(5) from DMO tower bottom of rectifying tower dimethyl oxalate component with through add Recycle hydrogen compressor pressurize after plant hydrogen mix after enter hydrogenator, in the presence of a hydrogenation catalyst, hydrogenation reaction methanol and ethylene glycol etc.; The temperature of hydrogenation reaction is 160 ~ 320 DEG C, and reaction pressure is 1 ~ 10MP, and liquid hourly space velocity is 1 ~ 3Kg/Kg.h;
(6) hydrogenation products enters the second gas-liquid separator generation gas-liquid separation, Recycle hydrogen compressor pressurization Posterior circle is added to hydrogenator described in gas phase portion warp, part enters membrane separation apparatus and return hydrogenator recycle after recycling, and liquid phase then enters the separation of ethylene glycol product tower and obtains ethylene glycol product.
Wherein,
Preferably, described oxonation device is externally connected with dehydration tower; The gas phase reclaimed through pressure-variable adsorption tank and from the methyl nitrite gas mixture of esterification column overhead after described dehydration tower removes moisture, then enter in oxonation device and carry out oxonation.
Preferably, described dehydration tower is made up of the mole sieve drier A of two alternate runs and regeneration and mole sieve drier B; Sorbent material is filled with in mole sieve drier A and mole sieve drier B; Described sorbent material is selected from 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 9A molecular sieve and calcium oxide.The service temperature of described mole sieve drier A and mole sieve drier B is 40 ~ 260 DEG C, and pressure is 1 ~ 10MPa.Unless otherwise indicated, in the present invention, all pressure all refers to gauge pressure.
Preferably, dry gas is obtained through dehydration tower process, moisture content 0.1 ~ 100ppm in dry gas.
Preferably, described oxonation device is externally connected with outlet heat exchanger I; Technical grade CO, N 2and from dehydration tower dry gas as oxonation raw material through described outlet heat exchanger I with carry out oxonation from entering again in oxonation device after the oxonation product heat exchange of oxonation device.
Preferably, the partial gas phase component from methanol wash column overhead enters esterification reaction tower again after the pressurization of carbonylation recycle compressor.
Preferably, described NO recovery tower top gaseous phase light constituent enters MN recovery tower again after compressor compression supercharging.
Preferably, described hydrogenator is externally connected with outlet heat exchanger II; Dimethyl oxalate component from DMO rectifying tower, the plant hydrogen from pressurized circulation compressor and circulation gas and from membrane separation apparatus recovery gas as hydrogenation reaction raw material through described outlet heat exchanger II with carry out hydrogenation reaction from entering again in hydrogenator after the hydrogenation products heat exchange of hydrogenator.
Preferably, first the liquid phase of described second gas-liquid separator separates enters method separation tower; The non-condensable gas of method separation tower recovered overhead enters described membrane separation apparatus, and the liquid phase light constituent parts such as the methyl alcohol of method separation tower recovered overhead enter the top of described Methanol Wash Column as washings, and part enters NO recovery tower; Method separation tower tower reactor liquid phase heavy constituent enters the further separating-purifying of light constituent rectifying tower; Light constituent rectifying tower tower top light constituent enters out-of-bounds alcohol retrieving arrangement recycling; Light constituent tower bottom of rectifying tower heavy constituent enters described ethylene glycol product tower; Ethylene glycol product column overhead light constituent enters out-of-bounds 1,2-BDO recycling and processing device and recycles further, and ethylene glycol product tower tower reactor heavy constituent enters out-of-bounds recycling and processing device and carries out subsequent disposal, and ethylene glycol product drawn by the top side line of ethylene glycol product tower.
Preferably, described second gas-liquid separator comprises high-pressure gas-liquid separator and low-pressure gas-liquid separator; Add Recycle hydrogen compressor described in entering through the isolated gas phase portion of high-pressure gas-liquid separator, part enters described low-pressure gas-liquid separator; The isolated liquid phase of high-pressure gas-liquid separator enters described method separation tower; Enter described membrane separation apparatus through the isolated gas phase of described low-pressure gas-liquid separator, enter described method separation tower through the isolated liquid phase of low-pressure gas-liquid separator.
Preferably, in the isolated gas phase of described high-pressure gas-liquid separator, wherein 0.1 ~ 10v% enters low-pressure gas-liquid separator.
Preferably, after methanol absorption tank absorption methyl alcohol, described membrane separation apparatus is entered through the isolated gas phase of described low-pressure gas-liquid separator and from the non-condensable gas of described separating methanol column overhead again.
Preferably, described oxonation device is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
Preferred, described carbonylation plate-type reactor is board-like fixed bed oxonation device.
Preferably, the center of described board-like fixed bed oxonation device is provided with plate groups lock chamber, is provided with plate groups in described plate groups lock chamber; The outer wall of described plate groups lock chamber to board-like fixed bed oxonation device inwall between be provided with beds; Oxonation catalyzer is filled with in beds; After oxonation raw material reaches beds inlet temperature, enter in beds from the top of described board-like fixed bed oxonation device and oxonation occurs; The refrigerant introduced from outside enters plate groups lock chamber from the bottom of board-like fixed bed oxonation device, and from the Base top contact of described board-like fixed bed oxonation device, counter-current process carries out the reaction heat that oxonation is taken away in heat exchange; Draw from the bottom of the carbonyl compounds bottom beds from board-like fixed bed oxonation device.
Preferably, described board-like fixed bed oxonation device is externally connected with drum I; The refrigerant introduced from outside enters drum I, and the refrigerant in drum I enters in the plate groups lock chamber of board-like fixed bed oxonation device and carries out heat exchange with beds, shifts out reaction heat; Refrigerant after heating is liquid-vapor mixture, enters drum I and carries out gas-liquid separation, and the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system and recycles.
Preferably, described oxonation catalyzer adopts Shanghai Wuzheng Engineering Co., Ltd. commercial catalyst, and the catalyst commercial product trade mark is DMO-0701T.
Preferably, described esterification reaction tower is packing tower;
Preferably, described esterification reaction tower is the column plate-filler mixing column simultaneously with deck portion and filler filling part.
Preferably, the number of theoretical plate of described esterification reaction tower is 20 ~ 50 pieces.It is first block of column plate that described each tower stage number sequential expression all sets tower top, then sequentially arranges by number to tower bottom.
Preferably, in the charging of described esterification reaction tower, described O 2divide 2 ~ 8 tunnels respectively from 16th ~ 50 pieces of column plate chargings; Described NO and from the top gaseous phase light constituent of Methanol Wash Column from 18th ~ 50 pieces of column plate chargings; Described fresh methanol, the recovery methyl alcohol from Methanol Recovery column overhead, the methyl alcohol from methanol rectifying tower recovered overhead and methyl nitrite mixture and from MN recovery tower tower reactor containing the alcoholic solution of methyl nitrite from 1st ~ 5 pieces of column plate chargings; Esterification reaction tower tower reactor backflow material is from 10th ~ 25 pieces of column plate chargings.
Preferably, in described esterification reaction tower, O 2, NO and methyl alcohol molar ratio be 0.01 ~ 0.8:0.1 ~ 3.2:0.8 ~ 50.
Preferably, described esterification column overhead temperatures is 30 ~ 80 DEG C, and bottom temperature is 50 ~ 200 DEG C, and reaction zone temperature is 50 ~ 160 DEG C, and reaction pressure is 0.5 ~ 10MPa.
Preferably, described methanol distillation column, Methanol Wash Column, methanol rectifying tower, nitric acid concentration tower, NO recovery tower, MN recovery tower, DMO rectifying tower are packing tower, tray column or bubble-plate column.
Preferably, the filler loaded in described packing tower is dumped packing or High Efficient Standard Packing; The shape of described dumped packing is the shape of a saddle, Raschig ring, Pall ring, wheel shape, rectangular saddle ring, spherical or column; Described High Efficient Standard Packing is ripple packing, grid packing or Impulse packing.
Preferably, the theoretical plate number of described methanol distillation column is 5 ~ 50 pieces, tower top temperature 40 ~ 150 DEG C, and bottom temperature is 60 ~ 230 DEG C, and tower top pressure is 0.01 ~ 2.0MPa.
Preferably, the reflux ratio of described Methanol Recovery column overhead light constituent is 0.1 ~ 3.0.
Preferably, in described methanol distillation column recovered overhead methyl alcohol, the part proportion that circulation enters esterification reaction tower is 10 ~ 90wt%.
Preferably, the theoretical plate number of described Methanol Wash Column is 10 ~ 50 pieces, and tower top temperature is 15 ~ 70 DEG C, and bottom temperature is 10 ~ 100 DEG C, and tower top pressure is 0.9 ~ 10MPa.
Preferably, in described Methanol Wash Column top gaseous phase component, the accounting of described periodic off-gases is 0.05 ~ 5v%.
Preferably, described methanol rectifying tower is extractive distillation column, and theoretical plate number is 10 ~ 60 pieces, and tower top temperature is 50 ~ 150 DEG C, and bottom temperature is 130 ~ 250 DEG C, and tower top pressure is 0.01 ~ 0.5MPa.
Preferably, the theoretical plate number of described nitric acid concentration tower is 1 ~ 30 piece, tower top temperature 30 ~ 110 DEG C, bottom temperature 60 ~ 160 DEG C, tower top pressure 0.01 ~ 0.3MPa.
Preferably, the reflux ratio of the tower top light constituent of described nitric acid concentration tower is 0.01 ~ 3.
Preferably, the theoretical plate number of described NO recovery tower is 5 ~ 30 pieces, and tower top temperature is 30 ~ 120 DEG C, and bottom temperature is 50 ~ 200 DEG C, and tower top pressure is 1 ~ 10MPa.
Preferably, described periodic off-gases is from 5th ~ 30 pieces of column plate chargings of NO recovery tower; Described concentrate nitric acid is from 1st ~ 10 pieces of column plate chargings of NO recovery tower; From the recovery methyl alcohol of separating methanol column overhead from 1st ~ 10 pieces of column plate chargings.
Preferably, in described NO recovery tower, the mol ratio of the NO in nitric acid, methyl alcohol and periodic off-gases is 1.1 ~ 10:2 ~ 100:1 ~ 5.
Preferably, the theoretical plate number of described MN recovery tower is 10 ~ 60 pieces, and tower top temperature is 0 ~ 50 DEG C, and bottom temperature is 0 ~ 80 DEG C, and reaction pressure is 1 ~ 10MPa.
Preferably, the theoretical plate number of described DMO rectifying tower is 10 ~ 50 pieces, and tower top temperature is 80 ~ 120 DEG C, and bottom temperature is 120 ~ 200 DEG C, normal pressure or decompression operation.
Preferably, described DMO rectifying tower tower top light constituent reflux ratio is 0.1 ~ 100.
Preferably, consisting of of the purified gas reclaimed in described pressure-variable adsorption tank: N 2be 60 ~ 80v%, CO be 20 ~ 40v%; Isolated CO 2gas accounts for 0.1 ~ 5v% of air inlet total amount, wherein CO 2concentration be 99.8 ~ 99.9v%; Isolated CO 2gas can through out-of-bounds device process.
Preferably, described hydrogenator is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
Preferred, described hydrogenation plate-type reactor is board-like fixed bed hydrogenation reactor.
Preferably, the center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, is provided with plate groups in described plate groups lock chamber; The outer wall of described plate groups lock chamber to board-like fixed bed hydrogenation reactor inwall between be provided with beds; Catalyst for hydrogenation is filled with in described beds; After hydrogenation reaction raw material reaches beds inlet temperature, enter in beds from the top of described board-like fixed bed hydrogenation reactor and hydrogenation reaction occurs; The refrigerant introduced from outside enters plate groups lock chamber from the bottom of board-like fixed bed hydrogenation reactor, and from the Base top contact of described board-like fixed bed hydrogenation reactor, counter-current process carries out the reaction heat that hydrogenation reaction is taken away in heat exchange; Draw from the bottom of the hydrogenation products bottom beds from board-like fixed bed hydrogenation reactor.
Preferably, described board-like fixed bed hydrogenation reactor is externally connected with drum II; The refrigerant introduced from outside enters drum II, and the refrigerant in drum II enters in the plate groups lock chamber of board-like fixed bed hydrogenation reactor and carries out heat exchange with beds, shifts out reaction heat; Refrigerant after heating is liquid-vapor mixture, enters drum II and carries out gas-liquid separation, and the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system and recycles.
Preferably, described refrigerant is water or thermal oil, is preferably water.
Preferably, described board-like fixed bed hydrogenation reactor is externally connected with the well heater that goes into operation; Go into operation the initial stage, temperature does not reach reaction requirement, and hydrogenation reaction raw material enters the well heater that goes into operation and carries out preheating, and preheating enters beds and carries out hydrogenation reaction after reaching beds temperature in; Go into operation the initial stage, described in the well heater that goes into operation provide unique thermal source for the hydrogenation reaction in described board-like fixed bed hydrogenation reactor; The thermal source of the described well heater that goes into operation is low-pressure steam.
Preferably, described catalyst for hydrogenation is selected from Shanghai Wuzheng Engineering Co., Ltd. commercial catalyst, and the catalyst commercial product trade mark is MEG-801T.
Preferably, the theoretical plate number of described method separation tower is 10 ~ 40 pieces, tower top temperature 40 ~ 70 DEG C, bottom temperature 80 ~ 180 DEG C, normal pressure or decompression operation; Described separating methanol column overhead light constituent reflux ratio is 0.1 ~ 3.
Preferably, the theoretical plate number of described light constituent rectifying tower is 10 ~ 60 pieces, tower top temperature 58 ~ 90 DEG C, bottom temperature 70 ~ 160 DEG C, absolute pressure of top of the tower 5 ~ 50KPa.
Preferably, the tower top light constituent reflux ratio of described light constituent rectifying tower is 1 ~ 50.
Preferably, the theoretical plate number of described ethylene glycol product tower is 30 ~ 100 pieces, the temperature of tower top 100 ~ 150 DEG C, bottom temperature 130 ~ 230 DEG C, and absolute pressure of top of the tower is 5 ~ 50KPa; Described ethylene glycol product column overhead light constituent reflux ratio is 50 ~ 120 or total reflux.
Preferably, described membrane separation apparatus is in parallel or be connected in series and form by 1 ~ 100 hollow fiber film assembly.
Preferably, the proof pressure of the shell of described membrane separation apparatus is 4.75MPa, maximum differential pressure 1.5MPa (unstripped gas is to infiltration gas); The service temperature of membrane separation apparatus is up to 85 DEG C.
Preferably, in the purification gas that membrane separation apparatus separating-purifying obtains, density of hydrogen is 88 ~ 99.00v%, hydrogen recovery rate 90 ~ 98.5%.
The ultimate principle of described membrane separation apparatus utilizes the partial pressure difference of hollow-fibre membrane both sides gas as impellent, by steps such as infiltration-dissolving-diffusion-parsings, utilizes hollow-fibre membrane different to the selective penetrated property of various gas, thus reach the object of separation.The shell side of hollow fiber film assembly made leave with rage by raw material, and tube side is made in infiltration leave with rage, and tail gas enters next hollow fiber film assembly.Because of H 2cH in film surface penetration speed 4, N 2, tens times of Ar etc., so H 2enter after collecting in every root hollow fiber conduit and discharge from membrane separation apparatus bottom, impermeable gas (tail gas) is discharged from the top of hollow fiber film assembly.Hollow fiber film assembly inside is a chipware be made up of 1000 ~ 100000 hollow-fibre membrane fiber tubes, and fibre pipe is processed through special by macromolecular material.Unstripped gas is entered by separator side mouth, just carry out dissolving, permeating and diffusion process on fibre wall along fiber tube bank lateral current downflow gas with gas during tunica fibrosa fiber tube exterior surface, utilize the difference in various gas dissolving, penetrating power, different types of gas delivery out.
Technique effect of the present utility model and advantage are:
Owing to adopting high top pressure operation in carbonylation system and esterification system, greatly can reduce maximization synthetic gas preparing ethylene glycol process unit to the requirement of equipment volume, be beneficial to single series device and produce maximization, be beneficial to equipment safety and produce and reduce facility investment.
Nitric acid waste utilization process and the coupling of periodic off-gases utilization process height, can be contained the raw material of a large amount of nitrogen protoxide periodic off-gases, generate the methyl nitrite needed for main reaction as recovery by circular treatment using the waste liquid produced in device.Process combination technological sciences are reasonable, realized the abundant recycle of discharging waste gas and waste liquid by a reactor, economic and environmental protection.
Described methyl nitrite is heat-sensitive substance, especially after higher than certain temperature, continue to raise with temperature, the decomposition of methyl nitrite can constantly aggravate, and the reaction of CO carbonylation coupling dimethyl oxalate is strong exothermal reaction, suitable reactor is adopted to keep the uniform temperature distribution of bed, controlling reaction hot(test)-spot temperature is the key preventing the decomposition of methyl nitrite and improve the yield of product, carbonylation plate-type reactor of the present invention is plate-type reactor, realize the reaction of CO carbonylation coupling dimethyl oxalate, the feature that temperature of reactor is evenly distributed can be made full use of, reach and improve dimethyl oxalate space-time yield and the feature of recycle reaction heat.Improve utilization coefficient and the reactor volume utilization ratio of catalyzer simultaneously, increase loaded catalyst, improve reactor throughput.Such reaction characteristics have also been obtained same energy conservation and consumption reduction effects in preparing ethylene glycol by using dimethyl oxalate plus hydrogen.
Valuable hydrogen resources has fully been saved in the recovery of described hydrogenation workshop section periodic off-gases, and then decreases unit coal consumption, is conducive to reducing the overall energy consumption of device and disposal of pollutants, has more real meaning.Meanwhile, the recovery of the hydrogenation workshop section periodic off-gases described in technique, the film separating system adopted reacting system pressure under equal load can reduce about 1MPa, and concerning compression system, the reduction of top hole pressure, can save a large amount of power consumptions.Fully save valuable hydrogen resources, and then decreased unit coal consumption, be conducive to reducing the overall energy consumption of device and disposal of pollutants, there is more real meaning.Adopt this film separating system, this is conducive to improving hydrogenation reaction speed, and ethylene glycol day output increased about 10% more originally.
In sum, by adopting high-pressure process flow process and plate-type reactor, effectively solving larger-scale unit bottleneck, reducing facility investment, by reclaiming heat of reaction waste heat, carrying out net heat recovery, unit ethylene glycol production energy consumption reduces, and reduces steam, consumption of cooling-water; By waste gas and waste stream process coupling, reduce toxic emission, thus reach the dual purpose of energy-saving and environmental protection.The complex energy that the present invention realizes the abundant reuse of discharging waste gas and waste liquid and device reaction heat, tower is separated uses, and improve efficiency of energy utilization, saving energy consumption, has significant industrial application value.To be synthetic gas preparing ethylene glycol technology provide guarantee to the technical development that environmental protection more, efficiency are higher, more energy-conservation in the present invention.Adopt the present invention's feasible and reasonable in economy technically.
Said apparatus system and optimization design can improve productive rate significantly, are that any document was not all recorded.And the technological process that the present invention proposes is also advantageous particularly viewed from energy consumption angle, there is the feature of remarkable energy efficient, connected applications useful matter circulation step, the particularly recycling of hydrogen in nitric acid waste utilization process and the coupling of periodic off-gases utilization process height and separating technology and reactor off-gas, effect is very significant.
Accompanying drawing explanation
A kind of commercial syngas pressure carbonylation of Fig. 1 produces dimethyl oxalate and the apparatus system (part) of Hydrogenation ethylene glycol
A kind of commercial syngas pressure carbonylation of Fig. 2 produces dimethyl oxalate and the apparatus system (part) of Hydrogenation ethylene glycol
Reference numeral:
1, oxonation device; 2, drum I; 3; Outlet heat exchanger I; 4, first gas-liquid separator; 5, methanol rectifying tower; 6, DMO rectifying tower; 7, Methanol Wash Column; 8, carbonylation recycle compressor; 9, esterification reaction tower; 10, dehydration tower; 11, methanol distillation column; 12, nitric acid concentration tower; 13, NO recovery tower; 14, compressor; 15, MN recovery tower; 16, pressure-variable adsorption tank; 17, hydrogenator; 18, drum II; 19, go into operation well heater; 20, outlet heat exchanger II; 21, high-pressure gas-liquid separator; 22, method separation tower; 23, light constituent rectifying tower; 24, ethylene glycol product tower; 25, add Recycle hydrogen compressor; 26, low-pressure gas-liquid separator; 27, methanol absorption tank; 28, membrane separation apparatus.
Embodiment
Below by way of specific specific examples, the technical solution of the utility model is described.Should be understood that one or more method stepss that the utility model is mentioned do not repel and before and after described combination step, also to there is additive method step or can also insert additive method step between these steps clearly mentioned; Should also be understood that these embodiments are only not used in restriction scope of the present utility model for illustration of the utility model.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the utility model of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the utility model.
The experimental technique of unreceipted actual conditions in embodiment below, usually conveniently condition, as: chemical industry operation handbook, or according to the condition that manufacturer advises.
Commercial syngas pressure carbonylation produces dimethyl oxalate and an apparatus system for Hydrogenation ethylene glycol, comprises oxonation system, esterification system, periodic off-gases spent acid coupling recovery system and hydrogenation reaction system;
Described oxonation system comprises oxonation device 1, first gas-liquid separator 4, Methanol Wash Column 7, methanol rectifying tower 5 and DMO rectifying tower 6; Described oxonation device 1 is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described first gas-liquid separator 4 is provided with opening for feed, pneumatic outlet and liquid exit; Described Methanol Wash Column 7 is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described methanol rectifying tower 5 is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described DMO rectifying tower 6 is provided with underfeed mouth, top exit and outlet at bottom;
Described esterification system comprises esterification reaction tower 9 and methanol distillation column 11; Described esterification reaction tower 9 is provided with its top feed mouth, upper feed inlet, multiple underfeed mouth, middle part reflux inlet, top exit and outlet at bottom; Described methanol distillation column 11 is provided with middle and lower part opening for feed, underfeed mouth, top exit and outlet at bottom;
Described periodic off-gases and spent acid coupling recovery system comprise nitric acid concentration tower 12, NO recovery tower 13, MN recovery tower 15 and pressure-variable adsorption tank 16; Described nitric acid concentration tower 12 is provided with middle part opening for feed, top exit and outlet at bottom; Described NO recovery tower 13 is provided with its top feed mouth, middle part opening for feed, bottom feed mouth, top exit and outlet at bottom; Described MN recovery tower 15 is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described pressure-variable adsorption tank 16 is provided with opening for feed, reclaims gas outlet and row's bleeder holes;
Described hydrogenation reaction system comprises and adds Recycle hydrogen compressor 14, hydrogenator 17, second gas-liquid separator, membrane separation apparatus 28, method separation tower 22, light constituent rectifying tower 23 and ethylene glycol product tower 24; The described Recycle hydrogen compressor 14 that adds comprises import and outlet; Described hydrogenation plate answers device 17 to be provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described second gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described membrane separation apparatus 28 is provided with opening for feed, reclaims gas outlet and row's bleeder holes; Described method separation tower 22 is provided with middle part opening for feed, the outlet of top non-condensable gas, top liquid phase light fraction outlet and the outlet of bottom liquid phases heavy constituent; Described light constituent rectifying tower 23 is provided with underfeed mouth, top exit and outlet at bottom; Described ethylene glycol product tower 24 is provided with underfeed mouth, top exit, upper outlet and outlet at bottom;
Its top feed mouth of described oxonation device 1 and CO feed conduit and N 2feed conduit connects through pipeline; The bottom discharge mouth of described oxonation device 1 is connected through pipeline with the opening for feed of described first gas-liquid separator 4; The pneumatic outlet of described first gas-liquid separator 4 is connected through pipeline with the underfeed mouth of described Methanol Wash Column 7; The liquid exit of described first gas-liquid separator 4 is connected through pipeline with the upper feed inlet of described methanol rectifying tower 5; The top exit of described Methanol Wash Column 7 is provided with branch outlet A and branch outlet B, and branch outlet A is connected through pipeline with a underfeed mouth of described esterification reaction tower 9, and branch outlet B is connected through pipeline with the bottom feed mouth of described NO recovery tower 13; The outlet at bottom of described Methanol Wash Column 7 is connected through pipeline with the underfeed mouth of described methanol rectifying tower 5; The top exit of described methanol rectifying tower 5 is connected through pipeline with the upper feed inlet of described esterification reaction tower 9; The outlet at bottom of described methanol rectifying tower 5 is connected through pipeline with the underfeed mouth of described DMO rectifying tower 6; The outlet at bottom of described DMO rectifying tower 6 is connected through pipeline with its top feed mouth of described hydrogenator 17, and the top exit of described DMO rectifying tower 6 is DMC products export;
Other underfeed mouth of described esterification reaction tower 9 and NO feed conduit and multichannel O 2feed conduit connects through pipeline respectively; Its top feed mouth of described esterification reaction tower 9 is connected through pipeline with methanol feedstock pipeline; The outlet at bottom of described esterification reaction tower 9 is provided with branch outlet C and branch outlet D, and branch outlet C is connected through pipeline with the middle part reflux inlet of described esterification reaction tower 9, and branch outlet D is connected through pipeline with the underfeed mouth of described methanol distillation column 11; The top exit of described esterification reaction tower 9 is connected through pipeline with its top feed mouth of described oxonation device 1; The top exit of described methanol distillation column 11 is provided with branch outlet E and branch outlet F, and branch outlet E is connected through pipeline with the upper feed inlet of described esterification reaction tower 9, and branch outlet F is connected through pipeline with the upper feed inlet of described MN recovery tower 15; The outlet at bottom of described methanol distillation column 11 is connected through pipeline with the middle part opening for feed of described nitric acid concentration tower 12;
The top exit of described nitric acid concentration tower 12 is waste liquid relief outlet; The outlet at bottom of described nitric acid concentration tower 12 is connected through pipeline with the middle part opening for feed of described NO recovery tower 13; The top exit of described NO recovery tower 13 is connected through pipeline with the underfeed mouth of described MN recovery tower 15; The outlet at bottom of described NO recovery tower 13 is connected through pipeline with the middle and lower part opening for feed of described methanol distillation column 11; The top exit of described MN recovery tower 15 is connected through pipeline with the opening for feed of described pressure-variable adsorption tank 16; The outlet at bottom of described MN recovery tower 15 is connected through pipeline with the upper feed inlet of described esterification reaction tower 9; The recovery gas outlet of described pressure-variable adsorption tank 16 is connected through pipeline with its top feed mouth of described carbonylation plate-type reactor 1; Row's bleeder holes of described pressure-variable adsorption tank 16 is connected through pipeline with out-of-bounds retrieving arrangement;
The described import adding Recycle hydrogen compressor 14 is connected through pipeline with plant hydrogen feed conduit, described in add Recycle hydrogen compressor 14 outlet be connected through pipeline with its top feed mouth of described hydrogenator 17; The bottom discharge mouth of described hydrogenator 17 is connected through pipeline with the opening for feed of described second gas-liquid separator; The pneumatic outlet of described second gas-liquid separator is provided with branch outlet G and branch outlet H, and branch outlet G is connected through pipeline with the described import adding Recycle hydrogen compressor 14, and branch outlet H is connected through pipeline with the opening for feed of described membrane separation apparatus 28; The liquid exit of described second gas-liquid separator is connected through pipeline with the underfeed mouth of described method separation tower 22; The top non-condensable gas outlet of described method separation tower 22 is connected through pipeline with the opening for feed of described membrane separation apparatus 28; The top liquid phase light fraction outlet of described method separation tower 22 is provided with branch outlet I and branch outlet J, and branch outlet I is connected through pipeline with the upper feed inlet of described Methanol Wash Column 7, and branch outlet J is connected through pipeline with its top feed mouth of described NO recovery tower 13; The bottom liquid phases heavy constituent outlet of described method separation tower 22 is connected through pipeline with the underfeed mouth of described light constituent rectifying tower 23; The top light fraction outlet of described light constituent rectifying tower 23 is connected through pipeline with out-of-bounds alcohol retrieving arrangement; The bottom heavy constituent outlet of described light constituent rectifying tower 23 is connected through pipeline with the underfeed mouth of described ethylene glycol product tower 24; The top exit of described ethylene glycol product tower 24 and out-of-bounds 1,2-BDO recycling and processing device connect through pipeline; The outlet at bottom of described ethylene glycol product tower 24 is connected through pipeline with out-of-bounds recycling and processing device; The upper outlet of described ethylene glycol product tower 24 is ethylene glycol product outlet; Row's bleeder holes of described membrane separation apparatus 28 is connected through pipeline with out-of-bounds retrieving arrangement, and the recovery gas outlet of described membrane separation apparatus 28 is connected through pipeline with its top feed mouth of described hydrogenator 17.
As one preferred embodiment, described oxonation device 1 is externally connected with dehydration tower 10; Described dehydration tower 10 is provided with opening for feed and dry gas outlet; The top exit of described esterification reaction tower 9 is connected through pipeline with the opening for feed of described dehydration tower 10 with the recovery gas outlet of described pressure-variable adsorption tank 16; The dry gas outlet of described dehydration tower 10 is connected through pipeline with described oxonation device 1 its top feed mouth.
Described dehydration tower is made up of the mole sieve drier A of two alternate runs and regeneration and mole sieve drier B; Filled with adsorbent in mole sieve drier A and mole sieve drier B.
As one preferred embodiment, the bottom discharge mouth of described oxonation device 1 is connected with outlet heat exchanger I 3; Described outlet heat exchanger I 3 is provided with cold logistics import, cold stream outlet, thermal material import and hot stream outlet; Described CO feed conduit, N 2the dry gas outlet of feed conduit and dehydration tower 10 is connected through pipeline with the cold logistics import of described outlet heat exchanger I 3; The cold stream outlet of described outlet heat exchanger I 3 is connected through pipeline with its top feed mouth of described oxonation device 1; The bottom discharge mouth of described oxonation device 1 is connected through pipeline with the hot logistics import of described outlet heat exchanger I 3; The hot stream outlet of described outlet heat exchanger I 3 is connected through pipeline with the opening for feed of described first gas-liquid separator 4.
As one preferred embodiment, described oxonation device 1 is externally connected with drum I 2; Described drum I 2 is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum I 2 is connected through pipeline with refrigerant feed conduit; The refrigerant exit of described drum I 2 is connected through pipeline with the bottom refrigerant import of described carbonylation plate-type reactor 1; The top refrigerant exit of described oxonation device 1 is connected through pipeline with the liquid-vapor mixture import of described drum I 2; The vapour outlet of described drum I 2 is connected through pipeline with out-of-bounds vapor-recovery system.
As one preferred embodiment, carbonylation recycle compressor 8 is connected with between the branch outlet A of described Methanol Wash Column 7 and the underfeed mouth of described esterification reaction tower 9; Described carbonylation recycle compressor 8 is provided with import and outlet; Described branch outlet A is connected through pipeline with the import of described carbonylation recycle compressor 8; The outlet of described carbonylation recycle compressor 8 is connected through pipeline with the underfeed mouth of described esterification reaction tower 9.
As one preferred embodiment, the top exit of described NO recovery tower 13 and the bottom feed mouth of described MN recovery tower 15 are connected with compressor 14; Described compressor 14 is provided with import and outlet; The top exit of described NO recovery tower 13 is connected through pipeline with the import of described compressor 14; The outlet of described compressor is connected through pipeline with the bottom feed mouth of described MN recovery tower 15.
As one preferred embodiment, the bottom discharge mouth of described hydrogenator 17 is connected with outlet heat exchanger II 20; Described outlet heat exchanger II 20 is provided with cold logistics import, cold stream outlet, thermal material import and hot stream outlet; The recovery gas outlet of the outlet at bottom of described DMO rectifying tower 6, described membrane separation apparatus 28 and described in add Recycle hydrogen compressor 25 the cold logistics import of outlet and described outlet heat exchanger II 20 be connected through pipeline; The cold stream outlet of described outlet heat exchanger II 20 is connected through pipeline with its top feed mouth of described hydrogenator 17; The bottom discharge mouth of described hydrogenator 17 is connected through pipeline with the hot logistics import of described outlet heat exchanger II 20; The hot stream outlet of described outlet heat exchanger II 20 is connected through pipeline with the opening for feed of described second gas-liquid separator.
As one preferred embodiment, its top feed mouth of described hydrogenator 17 is connected with the well heater 19 that goes into operation; The described well heater 19 that goes into operation is provided with opening for feed and discharge port; The cold stream outlet of described outlet heat exchanger II 20 is connected through pipeline with the described opening for feed going into operation well heater 19; The discharge port of the described well heater that goes into operation is connected through pipeline with its top feed mouth of described hydrogenator 17.
As one preferred embodiment, described hydrogenator 17 is externally connected with drum II 18; Described drum II 18 is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum II 18 is connected through pipeline with refrigerant feed conduit; The refrigerant exit of described drum II 18 is connected through pipeline with the bottom refrigerant import of described hydrogenator 17; The top refrigerant exit of described hydrogenator 17 is connected through pipeline with the liquid-vapor mixture import of described drum II 18; The vapour outlet of described drum II 18 is connected through pipeline with out-of-bounds vapor-recovery system.
As one preferred embodiment, described second gas-liquid separator comprises high-pressure gas-liquid separator 21 and low-pressure gas-liquid separator 26; Described high-pressure gas-liquid separator 21 is provided with opening for feed, pneumatic outlet and liquid exit; Described low-pressure gas-liquid separator 26 is provided with opening for feed, pneumatic outlet and liquid exit; The bottom discharge mouth of described hydrogenator 17 is connected through pipeline with the opening for feed of described high-pressure gas-liquid separator 21; The pneumatic outlet of described high-pressure gas-liquid separator 21 is provided with branch outlet K and branch outlet L, and branch outlet K is connected through pipeline with the described import adding Recycle hydrogen compressor 25, and branch outlet L is connected through pipeline with the opening for feed of described low-pressure gas-liquid separator 26; The liquid exit of described high-pressure gas-liquid separator 21 is connected through pipeline with the middle part opening for feed of described method separation tower 22; The pneumatic outlet of described low-pressure gas-liquid separator 26 is connected through pipeline with the opening for feed of described membrane separation apparatus 28; The liquid exit of described low-pressure gas-liquid separator 26 is connected through pipeline with the middle part opening for feed of described method separation tower 22.
As one preferred embodiment, methanol absorption tank 27 is provided with before the opening for feed of described membrane separation apparatus 28; Described methanol absorption tank 27 is provided with opening for feed and clean gas outlet; The pneumatic outlet of described low-pressure gas-liquid separator 26 is connected through pipeline with the opening for feed of described methanol absorption tank 27 with the top non-condensable gas outlet of described method separation tower 22; The clean gas outlet of described methanol absorption tank 27 is connected through pipeline with the opening for feed of described membrane separation apparatus 28.
Described oxonation device 1 can be plate-type reactor, tubular reactor or tubular type-board-like compound reactor;
As one preferred embodiment, described oxonation device 1 is board-like fixed bed oxonation device;
The center of described board-like fixed bed oxonation device is provided with plate groups lock chamber, and be provided with plate groups in described plate groups lock chamber, described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber to board-like fixed bed oxonation device inwall between be provided with beds; Be filled with oxonation catalyzer in beds, described beds is also provided with top entry and outlet at bottom; In the bottom of described board-like fixed bed oxonation device, the bottom refrigerant import of described board-like fixed bed oxonation device is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed oxonation device; At the top of described board-like fixed bed oxonation device, the its top feed mouth of described board-like fixed bed oxonation device is connected through pipeline with the top entry of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed oxonation device.
As one preferred embodiment, described esterification reaction tower 9 is packing tower;
As a kind of embodiment be more preferably, described esterification reaction tower 9 is the column plate-filler mixing column simultaneously with deck portion and filler filling part.
As one preferred embodiment, described Methanol Wash Column 7, methanol rectifying tower 5, methanol distillation column 11, NO recovery tower 13, MN recovery tower 15, DMO rectifying tower 6 and nitric acid concentration tower 12 is packing tower, tray column or bubble-plate column.
As one preferred embodiment, the filler loaded in described packing tower is dumped packing or High Efficient Standard Packing; The shape of described dumped packing is the shape of a saddle, Raschig ring, Pall ring, wheel shape, rectangular saddle ring, spherical or column; Described High Efficient Standard Packing is ripple packing, grid packing, Impulse packing.。
Described hydrogenation plate-type reactor 17 can be plate-type reactor, tubular reactor or tubular type-board-like compound reactor;
As one preferred embodiment, described hydrogenator 17 is board-like fixed bed hydrogenation reactor;
The center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, is provided with plate groups in described plate groups lock chamber, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber to board-like fixed bed hydrogenation reactor inwall between be provided with beds; Be filled with catalyst for hydrogenation in described beds, described beds is also provided with top entry and outlet at bottom; In the bottom of described board-like fixed bed hydrogenation reactor, the bottom refrigerant import of described board-like fixed bed hydrogenation reactor is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed hydrogenation reactor; At the top of described board-like fixed bed hydrogenation reactor, the its top feed mouth of described board-like fixed bed hydrogenation reactor is connected through pipeline with the top entry of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed hydrogenation reactor.
As one preferred embodiment, described membrane separation apparatus 28 is in parallel or be connected in series and form by 1 ~ 100 hollow fiber film assembly.
As shown in Figure 1 and Figure 2, for utilizing a kind of commercial syngas pressure carbonylation provided by the utility model to produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol carries out the technical process of producing:
The O of the NO from pipeline 18, the fresh methanol from pipeline 26 and point 2 ~ 8 tunnel chargings 2in esterification reaction tower 9, carry out gas-liquid counter current contact esterification occurs, the MN gas mixture that tower top generates is through pipeline 23 and enter dehydration tower 10 through pipeline 24 after converging from the recovery gas phase of the pressure-variable adsorption tank of pipeline 39 and carry out processed, the dry gas after dehydration through pipeline 25 with from the CO of the pipeline 1 and N of pipeline 2 2pipeline 3 is entered as oxonation unstripped gas after mixing.Tower reactor in esterification reaction tower 9 is the acid waste liquid containing a large amount of methyl alcohol, except being back to esterification reaction tower 9 by a certain amount of by pipeline 20, all the other acid waste liquids enter methanol distillation column 11 by pipeline 21 with the methyl alcohol acid waste liquid simultaneously from pipeline 33 and carry out Methanol Recovery; The methyl alcohol light constituent that methanol distillation column 11 tower top produces is shunted after piping 28, do except washings except a part is entered in MN recovery tower 15 by pipeline 29, other parts with the fresh methanol from pipeline 26, by the alcohol source of pipeline 22 as esterification reaction tower 9; The acid-bearing wastewater that methanol distillation column 11 tower reactor produces enters nitric acid concentration tower 12 by pipeline 27 and carries out nitric acid concentrate.
From the oxonation raw material of pipeline 3 through outlet heat exchanger I 3 with after the oxonation product heat exchange of oxonation device 1 bottom discharge, enter beds from the top of oxonation device 1 and carry out oxonation; Enter in drum I 2 from the Purified Water outside system by pipeline 8 simultaneously, refrigerant in drum I 2 bottom oxonation device 1, enters plate groups lock chamber by pipeline 9 and beds carries out heat exchange, shift out the heat that reaction produces, refrigerant after heating is liquid-vapor mixture, after the Base top contact of oxonation device 1, enter drum I 2 carry out gas-liquid separation, the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system by pipeline 7 and recycles.Oxonation product enters the first gas-liquid separator 4 and gas-liquid separation occurs after the heat exchange of outlet heat exchanger I 3, gaseous component containing most of DMC (methylcarbonate) enters Methanol Wash Column 7 through pipeline 11, and with the recovery methyl alcohol counter current contact from pipeline 57; The methyl alcohol washing lotion of the first gas-liquid separator 4 tower reactor DMO heavy constituent containing MN (methyl nitrite), DMC and DMO (dimethyl oxalate) in pipeline 10 and Methanol Wash Column 7 tower reactor enters methanol rectifying tower 5 through pipeline 12, two bursts of logistics counter current contact, carry out extracting and separating; The gas phase light constituent major part of Methanol Wash Column 7 tower top enters esterification reaction tower 9 recycle by carbonylation recycle compressor 8 through pipeline 17, and small part enters NO recovery tower 13 as periodic off-gases through piping 32 and recycles; The methyl alcohol of methanol rectifying tower 5 recovered overhead and methyl nitrite mixture are circulated to esterification reaction tower 9 by pipeline 14 and recycle, and tower reactor heavy constituent enters DMO rectifying tower 6 by pipeline 13; DMO rectifying tower 6 tower top obtains DMC product, and tower reactor dimethyl oxalate component enters the raw material of pipeline 15 as hydrogenation reaction.
Nitric acid concentration tower 12 tower top is mainly acid-bearing wastewater and is drained into outside battery limit (BL) by pipeline 30 and carry out environmental protection treatment, the concentrated nitric acid of concentrate at the bottom of tower through pipeline 31 enter NO recovery tower 13 as acid source and the recovery methyl alcohol from pipeline 57 with the periodic off-gases counter current contact generation esterification regenerative response from pipeline 32 to reclaim the NO in periodic off-gases; The nitric acid waste that NO recovery tower 13 tower reactor contains methyl alcohol enters into methanol distillation column 11 by pipeline 33 and carries out circulation and stress, and the light constituent containing MN that tower top generates then enters MN recovery tower 15 after compressor 14 supercharging.With the recovery methyl alcohol counter current contact from pipeline 29 in MN recovery tower 15, wash away MN wherein, and enter esterification reaction tower 9 from tower reactor through piping 36, top gaseous phase light constituent enters pressure-variable adsorption tank 16 by pipeline 37, through pressure-variable adsorption, removes CO 2after enter dehydration tower 10 containing the gas mixture of CO by pipeline 39, and the CO removed 2gas can be used as to be disposed to outside battery limit (BL) and processes.
Pipeline 55 is entered through adding after Recycle hydrogen compressor 25 pressurizes after plant hydrogen from pipeline 54 and the mixing of the circulation gas from pipeline 53, then with from pipeline 15 dimethyl oxalate component and mix as hydrogenation reaction raw material from the recover hydrogen of pipeline 68, outlet heat exchanger II 20 is entered from pipeline 40, carry out heat exchange with the hydrogenation reaction product of drawing bottom hydrogenator 17, then enter beds from the tower top of hydrogenator 17 and carry out catalytic hydrogenation reaction; Meanwhile, drum II 18 is entered by pipeline 48 from the Purified Water outside system, refrigerant in drum II 18 enters plate groups lock chamber by pipeline 49 from the bottom of hydrogenator 17 and beds carries out heat exchange, shift out the heat that reaction produces, refrigerant after heating is liquid-vapor mixture, after the Base top contact of hydrogenator 17, enter drum II 18 carry out gas-liquid separation, the low-pressure saturated steam of generation enters out-of-bounds low-pressure steam recovery system by pipeline 47 and recycles.Hydrogenation reaction product enters high-pressure gas-liquid separator 21 from pipeline 44 and carries out gas-liquid separation after heat exchange, gas phase portion major part after piping 51 enters pipeline 53 as circulation gas and circulates, and remains a part of gas and enters low-pressure gas-liquid separator 26 by pipeline 52 and carry out gas-liquid separation; Liquid Phase Methanol in low-pressure gas-liquid separator 26 is flowed out by pipeline 64, gas phase portion is then by pipeline 65 with enter methanol absorption tank 27 by pipeline 66 after converging from the non-condensable gas of pipeline 58 and carry out further methanol removal, gas after de-liquid enters membrane separation apparatus 28 from pipeline 67, through the recycling of membranous system, except sub-fraction CO 2, CO and CH 4speed to put from pipeline 69 Deng not condensing, the H that major part reclaims 2pipeline 68 recycle is entered after supercharging.
The thick product of liquid phase ethylene glycol separated from high-pressure gas-liquid separator 21 flows out from pipeline 50, through with converge from pipeline 64 Liquid Phase Methanol after enter method separation tower 22; Method separation tower 22 tower top is speeded to put a certain amount of not condensing by pipeline 58 and is reclaimed, and tower top liquid phase light constituent enters pipeline 57, and the tower bottoms piping 56 that communicates enters in light constituent rectifying tower 23 and is separated; The light constituents such as light constituent rectifying tower 23 tower top light constituent ethanol, methyl glycolate enter alcohol retrieving arrangement outside battery limit (BL) by pipeline 60 and reclaim, tower reactor polyol blends is then entered in ethylene glycol product tower 24 by pipeline 59 and is further purified, wherein mainly containing 1, the mixing light constituent of 2-BDO, ethylene glycol is recycled further by pipeline 63, the ethylene glycol of tower body top side line output is by pipeline 62 as product extraction, and tower reactor is that the mixture containing a small amount of ethylene glycol and ethylene glycol polycondensate enters outside battery limit (BL) and processes.
The driving initial stage, the use well heater 19 pairs of hydrogenation reaction raw materials that go into operation heat, thermal source adopts low-pressure steam, and the hydrogenating materials from pipeline 40 enters pipeline 45 and after the well heater 19 that goes into operation is preheated to bed inlet temperatures, enters beds through pipeline 46 and pipeline 42 from the top of hydrogenator 17 carries out hydrogenation reaction.
Above-mentioned technical process is utilized to carry out industrial example as follows:
From the tower top light constituent (composition: MN:5.22v%, CO:22.12v%, N of Methanol Wash Column 2: 58.5v%, NO:11.14v%, CO 2: 0.63v%, methyl alcohol 1.57v%, other: 0.82v%) and from entering esterification reaction tower 9 (tower plate structure is packing tower for internal diameter 50mm, height 2600mm, theoretical plate number 25) after the NO mixing outside battery limit (BL) from the 25th piece of column plate charging, O 23 tunnels are divided to enter esterification reaction tower 9 from the 22nd, the 23rd and the 25th block of column plate respectively, with the methyl alcohol reclaimed from methanol rectifying tower 5 of the fresh methanol from tower top the 1st piece of column plate charging and the recovery methyl alcohol mixed liquor from methanol distillation column 11, the 5th piece of charging and methyl nitrite mixture and from MN recovery tower 15 tower reactor the alcoholic solution containing methyl nitrite and in tower, carry out gas-liquid counter current from the tower reactor phegma of the 10th piece of charging and contact, there is esterification (wherein O 2, NO and methyl alcohol mol ratio be: 0.1:0.6:50).Esterification reaction tower 9 tower top temperature is 50 DEG C, and bottom temperature is 93 DEG C, and reaction zone temperature is 70 ± 10 DEG C, and reaction pressure is 2MPa.Esterification reaction tower 9 tower reactor discharging (composition: methyl alcohol: 71.8wt%, MN:8.0wt%, other heavy constituent 20.2wt% such as the acid that reaction generates and water) enters methanol distillation column 11 and recycles after extraction.Esterification reaction tower 9 top gaseous phase component (composition: MN:10.05v%, CO:26.42v%, N 2: 55.88v%, NO:5.2v%, CO 2: 0.60v%, methyl alcohol 1.57v%, other: 0.28v%) then enter dehydration tower 10 and dewater.After the dehydration of dehydration tower 10 (sorbent material is 4A molecular sieve, service temperature: 43 DEG C: pressure: 1.9MPa, two mole sieve drier A and mole sieve drier B alternate run and regeneration), obtain the dry gas that water content is 60ppm.
The useless alcohol liquid of acid that contains of esterification reaction tower 9 tower reactor enters methanol distillation column 11 (internal diameter 50mm, height 2100mm, theoretical plate number 20 pieces, in-built High Efficient Standard Packing, tower top temperature 120 DEG C, column bottom temperature is 140 DEG C, tower top pressure 0.7MPa, the reflux ratio 1.2 of tower top light constituent, tower top is the light constituent (component: methyl alcohol: 90wt% containing methyl alcohol, MN:8wt%, H 2o:2wt%) part (accounting 75wt%) and supplementary fresh methanol are converged, and enter the top of esterification reaction tower 9, remain as the washings in MN recovery tower 15; Methanol distillation column 11 tower reactor acid-bearing wastewater enters nitric acid concentration tower 12 and carries out nitric acid concentrate.
Oxonation device 1 (height is 2000mm for board-like fixed-bed reactor, internal diameter: 320mm), center is provided with plate groups lock chamber, is provided with 3 groups of plates in plate groups lock chamber, often organizes 3 pieces of plates; The outer wall of plate groups lock chamber is provided with beds between oxonation device 1 inwall, interior filling carbonylation reaction under high pressure catalyzer (Shanghai Wuzheng Engineering Co., Ltd. commercial catalyst, the catalyst commercial product trade mark is DMO-0701T).Dry gas from dehydration tower 10 and the postindustrial level CO of Dehydroepiandrosterone derivative (99v%) as oxonation raw material and after mixing as the nitrogen of inertia source of the gas after exporting heat exchanger I 3 and the heat exchange of oxonation product, be preheated to 95 DEG C, first enter from the top of oxonation device 1, then enter beds through radial flow mode and carry out oxonation (beds hot(test)-spot temperature 130 DEG C, reaction pressure is 1.8MPa, and gas hourly space velocity is 10000h -1); Carbonyl compounds enters the first gas-liquid separator 4 after then entering the heat exchange of outlet interchanger 3, carries out gas-liquid separation at this.
Described oxonation device 1 plate groups lock chamber refrigerant is water medium.Enter drum I 2 from the Purified Water outside system and supplement water inlet, water in drum I enters plate groups lock chamber and beds in oxonation device 1 and carries out heat exchange, shift out the heat that reaction produces, water after heating is liquid-vapor mixture, enter drum and carry out gas-liquid separation, the low-pressure saturated steam of generation is sent to low-pressure steam pipe network outside battery limit (BL) and recycles.
The liquid phase (methyl alcohol: 1.16wt%, DMC:0.45wt%, DMO:97.6wt%, other 0.79wt%) that first gas-liquid separator 4 is drawn enters in methanol rectifying tower 5 as extraction agent and is separated; The gas mixture phase component containing DMC of drawing enters Methanol Wash Column 7 (internal diameter: 50mm, height is 3200mm, number of theoretical plate is 30 pieces, in-built High Efficient Standard Packing, tower top temperature is 28.1 DEG C, bottom temperature is 39.8 DEG C, tower top pressure is 1.5MPa) by reclaiming methyl alcohol (content 99.9wt%) counter current contact with method separation tower 22, by DMC and the DMO wash-out in gas mixture, the gas phase light constituent major part at Methanol Wash Column 7 top enters esterification reaction tower 9 by carbonylation recycle compressor 8, and the oxynitride that oxonation generates is carried out recycle; Small part non-condensable gas (gas accounting 0.5v%) enters NO recovery tower 13 as periodic off-gases and recycles; Methanol Wash Column 7 tower reactor liquid phase enters in methanol rectifying tower 5 and is separated.
Methanol rectifying tower 5 (internal diameter: 50mm, height is 2600mm, extractive distillation column, number of theoretical plate is 25 pieces, in-built High Efficient Standard Packing, and tower top temperature is 73.12 DEG C, bottom temperature is 185.0 DEG C, tower top pressure is 0.1MPa) light constituent (methyl alcohol: 88.2wt%, MN:11.8wt%) of tower top enters esterification reaction tower 9 as one of alcohol source, and the heavy constituent containing DMC with DMO in tower reactor enters DMO rectifying tower 6 and is separated.
DMO rectifying tower 6 (internal diameter: 50mm, height is 3000mm, and number of theoretical plate is 28 pieces, in-built High Efficient Standard Packing, tower top temperature 103 DEG C, bottom temperature 180 DEG C, atmospheric operation, reflux ratio 50), tower top DMC carries out collecting (DMC product purity is 99.41wt%) as product; Tower reactor heavy constituent (DMO purity is 99.9wt%) is all as the raw material of hydrogenation workshop section.
Described nitric acid concentration tower 12 (internal diameter 32mm, height 850mm, theoretical plate number 8 pieces, in-built High Efficient Standard Packing, tower top temperature 64 DEG C, bottom temperature is 87 DEG C, tower top pressure 0.15MPa, reflux ratio 0.05) in, tower top is mainly acid-bearing wastewater and drains into outside battery limit (BL) and carry out environmental protection treatment, it is the concentrated nitric acid of 68wt% that tower reactor concentrate produces concentration, as the acid source of NO recovery tower 13.
NO recovery tower 13 (internal diameter: 32mm, height is 2100mm, number of theoretical plate is 20 pieces, in-built High Efficient Standard Packing, tower top temperature is 50 DEG C, bottom temperature is 100 DEG C, tower top pressure is 1.4MPa) in, the described periodic off-gases from Methanol Wash Column 7 from the 20th piece of column plate charging, the recovery methyl alcohol (99.9wt%) from method separation tower 22 from the 1st piece of column plate charging and the concentrated nitric acid counter current contact generation esterification regenerative response from nitric acid concentration tower 12 from the 8th piece of column plate charging.HNO in described periodic off-gases in NO, concentrate nitric acid 3, methyl alcohol mol ratio be 1:2.5:20.Tower top light constituent (the composition: CO:21.1v%, CO of NO recovery tower 13 2: 0.6v%, MN:20.8v%, N 2: 55.7v%, methyl alcohol: 1.8v%) enter MN recovery tower 15 through compressor 14 supercharging; The 3rd block of column plate that NO recovery tower 13 tower reactor heavy constituent (composition: methyl alcohol 71.8wt%, other heavy constituent 28.2wt% such as the acid that reaction generates and water) enters methanol distillation column 11 reclaims.
MN recovery tower 15 (internal diameter: 32mm, height is 3200mm, number of theoretical plate is 30 pieces, in-built High Efficient Standard Packing, tower top temperature is 30.8 DEG C, and bottom temperature is 41.3 DEG C, tower top pressure is 2MPa) in charging with from the recovery methyl alcohol counter current contact coming from methanol distillation column 11 of the 1st piece of column plate charging, absorb a large amount of MN in air inlet, remaining gas (composition: CO:27.3v%, CO 2: 0.8v%, N 2: 71.9v%) enter pressure-variable adsorption tank 16 from tower top, the 5th block of column plate that the material (composition: methyl alcohol: 79.3mol%, MN:20.7mol%) in tower reactor then enters esterification reaction tower 9 is recycled.The top gaseous phase of described MN recovery tower 15 through pressure-variable adsorption tank 16 pressure-variable adsorption, purified gas (N 2: 72v%, CO:28v%) enter dehydration tower 10 process after enter oxonation device 1, and by 0.95v% gas (composition: CO 2for 99.8v%) be disposed to outside battery limit (BL) and process.
Hydrogenator 17 (height is 900mm for board-like fixed bed hydrogenation reactor, internal diameter: 325mm), center is provided with plate groups lock chamber, is provided with three groups of plates in plate groups lock chamber, often organizes 3 pieces of plates; The outer wall of plate groups lock chamber is provided with beds between hydrogenator inwall, in-builtly fills out catalyst for hydrogenation: Shanghai Wuzheng Engineering Co., Ltd. commercial catalyst, and the catalyst commercial product trade mark is MEG-801T).
Technical grade H 2(purity is 99.9v%) and the circulation gas (composition: hydrogen 96v% from high-pressure gas-liquid separator 21, methane 0.05v%, nitrogen 0.02v%, carbon monoxide 0.02v%, methyl alcohol 3v%, other 0.91v%) through add Recycle hydrogen compressor 25 compress after with converge from the dimethyl oxalate (99.9%wt) of DMO rectifying tower 6 tower reactor after enter hydrogenation plate-type reactor 17 outlet heat exchanger II 20 be preheated to 175 DEG C after, first enter from the top of hydrogenator 17, then enter beds through radial flow mode and carry out hydrogenation reaction (beds hot(test)-spot temperature 190 DEG C, reaction pressure is 3.0MPa, liquid hourly space velocity is 2.8Kg/Kg.h), hydrogenation products enters high-pressure gas-liquid separator 21 after the heat exchange of bottom discharge laggard inlet/outlet heat exchanger II 20, carries out gas-liquid separation at this.
Go into operation the initial stage, the material through exporting heat exchanger II 20 enters the well heater 19 that goes into operation and carries out preheating, and the gas after preheating enters beds after reaching beds temperature in as unstripped gas and carries out hydrogenation reaction.
Hydrogenator 17 plate groups lock chamber refrigerant is water medium.Enter drum II 18 from the Purified Water outside system and supplement water inlet, water in drum II 18 enters plate groups lock chamber and beds in hydrogenator 17 and carries out heat exchange, shift out the heat that reaction produces, water after heating is liquid-vapor mixture, enter drum II and carry out gas-liquid separation, the low-pressure saturated steam of generation is sent to low-pressure steam pipe network outside battery limit (BL) and recycles.
Hydrogenation products is after high-pressure gas-liquid separator 21 is separated, gas phase major part enters as circulation gas and adds Recycle hydrogen compressor 25, residue non-condensable gas (gas accounting 1.2v%) enters low-pressure gas-liquid separator 26, liquid phase (the methyl alcohol: 50.1wt% that high-pressure gas-liquid separator 21 is drawn, ethylene glycol: 48.55wt%, methyl glycolate: 0.06wt%, ethanol: 0.39wt%, BDO:0.12wt%, other 0.78wt%) enter in method separation tower 22 and be separated.The liquid phase that low-pressure gas-liquid separator 26 is separated enters in method separation tower 22 and is separated, gas phase is through methanol absorption tank 27 (internal diameter 160mm, height 900mm) further after methanol removal, gas phase (composition: hydrogen 97v% wherein, methane 0.15v%, nitrogen 0.06v%, carbon monoxide 0.27v%, other 2.52v%) enter membrane separation apparatus 28 and recycle.Hydrogen (purity is 99.9v%) after membrane separation apparatus is separated enters hydrogenation plate-type reactor 17 after the preheating of outlet heat exchanger II, only has the non-condensable gases such as small part methane rich to discharge as periodic off-gases and out-of-bounds reclaims again.
Method separation tower 22 (internal diameter: 50mm, height is 2600mm, number of theoretical plate is 25 pieces, in-built High Efficient Standard Packing, tower top temperature is 50.82 DEG C, bottom temperature is 171 DEG C, absolute pressure of top of the tower is 90kPa) in, material is the 12nd piece of column plate place charging, tower top non-condensable gas enters after methanol absorption tank 27 processes and enters membrane separation apparatus 28, trim the top of column, than 1.6, enters Methanol Wash Column 7 and NO recovery tower 13 after tower top discharging (methyl alcohol of 99.9wt%, other low boiling point component of 0.1wt%) extraction respectively; Method separation tower 22 tower reactor heavy constituent (composition: 96wt% ethylene glycol, 0.12wt% methyl glycolate, 2.68wt%1.2-BDO, 0.8wt% ethanol, other component of 0.4wt%) enters light constituent rectifying tower 23.
Light constituent rectifying tower 23 (internal diameter: 50mm, height is 4000mm, number of theoretical plate is 40 pieces, in-built High Efficient Standard Packing, tower top temperature 83.8 DEG C, bottom temperature 146.9 DEG C, absolute pressure of top of the tower 16kPa, trim the top of column is than 50), the tower top extraction thick product of ethanol (98wt% ethanol, 2wt% methyl glycolate) is delivered to outside battery limit (BL) and is carried out collection and treatment; In tower reactor heavy constituent (97.9wt% ethylene glycol, 2.1wt%1.2-BDO) ethylene glycol product tower 24.
Ethylene glycol product tower 24 (internal diameter 50mm, height 6500mm, tower number of theoretical plate 60 pieces, in-built High Efficient Standard Packing, tower top temperature 130 DEG C, bottom temperature is 170.1 DEG C, absolute pressure of top of the tower 5kPa) in, trim the top of column is than 98, and (component: 1,2-BDO is 19.79wt% to overhead extraction; Ethylene glycol is 80wt%, other 0.21wt%) reclaim as byproduct to battery limit (BL), tower reactor is for carrying out processing outside battery limit (BL) containing a small amount of ethylene glycol and ethylene glycol polycondensate, and ethylene glycol product tower 24 tower body side line the 5th piece of column plate place be extraction the finished product ethylene glycol (content is 99.99wt%) then.
Above-described embodiment is exemplary illustration principle of the present utility model and effect only, but not for limiting the utility model.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, have in all art and usually know that the knowledgeable modifies or changes not departing from all equivalences completed under the spirit and technological thought that the utility model discloses, must be contained by claim of the present utility model.

Claims (19)

1. commercial syngas mesohigh carbonylation produces dimethyl oxalate an apparatus system for Hydrogenation ethylene glycol, it is characterized in that, comprises oxonation system, esterification system, periodic off-gases and to be coupled with spent acid recovery system and hydrogenation reaction system;
Described oxonation system comprises oxonation device (1), the first gas-liquid separator (4), Methanol Wash Column (7), methanol rectifying tower (5) and dimethyl oxalate rectifying tower (6); Described oxonation device (1) is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described first gas-liquid separator (4) is provided with opening for feed, pneumatic outlet and liquid exit; Described Methanol Wash Column (7) is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described methanol rectifying tower (5) is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described dimethyl oxalate rectifying tower (6) is provided with underfeed mouth, top exit and outlet at bottom;
Described esterification system comprises esterification reaction tower (9) and methanol distillation column (11); Described esterification reaction tower (9) is provided with its top feed mouth, upper feed inlet, multiple underfeed mouth, middle part reflux inlet, top exit and outlet at bottom; Described methanol distillation column (11) is provided with middle and lower part opening for feed, underfeed mouth, top exit and outlet at bottom;
The described periodic off-gases recovery system that is coupled with spent acid comprises nitric acid concentration tower (12), NO recovery tower (13), methyl nitrite recovery tower (15) and pressure-variable adsorption tank (16); Described nitric acid concentration tower (12) is provided with middle part opening for feed, top exit and outlet at bottom; Described NO recovery tower (13) is provided with its top feed mouth, middle part opening for feed, bottom feed mouth, top exit and outlet at bottom; Described methyl nitrite recovery tower (15) is provided with upper feed inlet, underfeed mouth, top exit and outlet at bottom; Described pressure-variable adsorption tank (16) is provided with opening for feed, reclaims gas outlet and row's bleeder holes;
Described hydrogenation reaction system comprises and adds Recycle hydrogen compressor (14), hydrogenator (17), the second gas-liquid separator, membrane separation apparatus (28), method separation tower (22), light constituent rectifying tower (23) and ethylene glycol product tower (24); The described Recycle hydrogen compressor (14) that adds comprises import and outlet; Described hydrogenator (17) is provided with its top feed mouth, bottom discharge mouth, bottom refrigerant import and top refrigerant exit; Described second gas-liquid separator is provided with opening for feed, pneumatic outlet and liquid exit; Described membrane separation apparatus (28) is provided with opening for feed, reclaims gas outlet and row's bleeder holes; Described method separation tower (22) is provided with middle part opening for feed, the outlet of top non-condensable gas, top liquid phase light fraction outlet and the outlet of bottom liquid phases heavy constituent; Described light constituent rectifying tower (23) is provided with underfeed mouth, top exit and outlet at bottom; Described ethylene glycol product tower (24) is provided with underfeed mouth, top exit, upper outlet and outlet at bottom;
Its top feed mouth of described oxonation device (1) and CO feed conduit and N 2feed conduit connects through pipeline; The bottom discharge mouth of described oxonation device (1) is connected through pipeline with the opening for feed of described first gas-liquid separator (4); The pneumatic outlet of described first gas-liquid separator (4) is connected through pipeline with the underfeed mouth of described Methanol Wash Column (7); The liquid exit of described first gas-liquid separator (4) is connected through pipeline with the upper feed inlet of described methanol rectifying tower (5); The top exit of described Methanol Wash Column (7) is provided with branch outlet A and branch outlet B, branch outlet A is connected through pipeline with a underfeed mouth of described esterification reaction tower (9), and branch outlet B is connected through pipeline with the bottom feed mouth of described NO recovery tower (13); The outlet at bottom of described Methanol Wash Column (7) is connected through pipeline with the underfeed mouth of described methanol rectifying tower (5); The top exit of described methanol rectifying tower (5) is connected through pipeline with the upper feed inlet of described esterification reaction tower (9); The outlet at bottom of described methanol rectifying tower (5) is connected through pipeline with the underfeed mouth of described dimethyl oxalate rectifying tower (6); The outlet at bottom of described dimethyl oxalate rectifying tower (6) is connected through pipeline with its top feed mouth of described hydrogenator (17), and the top exit of described dimethyl oxalate rectifying tower (6) is methylcarbonate products export;
Other underfeed mouth of described esterification reaction tower (9) and NO feed conduit and multichannel O 2feed conduit connects through pipeline respectively; Its top feed mouth of described esterification reaction tower (9) is connected through pipeline with methanol feedstock pipeline; The outlet at bottom of described esterification reaction tower (9) is provided with branch outlet C and branch outlet D, branch outlet C is connected through pipeline with the middle part reflux inlet of described esterification reaction tower (9), and branch outlet D is connected through pipeline with the underfeed mouth of described methanol distillation column (11); The top exit of described esterification reaction tower (9) is connected through pipeline with its top feed mouth of described oxonation device (1); The top exit of described methanol distillation column (11) is provided with branch outlet E and branch outlet F, branch outlet E is connected through pipeline with the upper feed inlet of described esterification reaction tower (9), and branch outlet F is connected through pipeline with the upper feed inlet of described methyl nitrite recovery tower (15); The outlet at bottom of described methanol distillation column (11) is connected through pipeline with the middle part opening for feed of described nitric acid concentration tower (12);
The top exit of described nitric acid concentration tower (12) is waste liquid relief outlet; The outlet at bottom of described nitric acid concentration tower (12) is connected through pipeline with the middle part opening for feed of described NO recovery tower (13); The top exit of described NO recovery tower (13) is connected through pipeline with the underfeed mouth of described methyl nitrite recovery tower (15); The outlet at bottom of described NO recovery tower (13) is connected through pipeline with the middle and lower part opening for feed of described methanol distillation column (11); The top exit of described methyl nitrite recovery tower (15) is connected through pipeline with the opening for feed of described pressure-variable adsorption tank (16); The outlet at bottom of described methyl nitrite recovery tower (15) is connected through pipeline with the upper feed inlet of described esterification reaction tower (9); The recovery gas outlet of described pressure-variable adsorption tank (16) is connected through pipeline with its top feed mouth of described oxonation device (1); Row's bleeder holes of described pressure-variable adsorption tank (16) is connected through pipeline with out-of-bounds retrieving arrangement;
The described import adding Recycle hydrogen compressor (14) is connected through pipeline with plant hydrogen feed conduit, described in add Recycle hydrogen compressor (14) outlet be connected through pipeline with its top feed mouth of described hydrogenator (17); The bottom discharge mouth of described hydrogenator (17) is connected through pipeline with the opening for feed of described second gas-liquid separator; The pneumatic outlet of described second gas-liquid separator is provided with branch outlet G and branch outlet H, branch outlet G is connected through pipeline with the described import adding Recycle hydrogen compressor (14), and branch outlet H is connected through pipeline with the opening for feed of described membrane separation apparatus (28); The liquid exit of described second gas-liquid separator is connected through pipeline with the underfeed mouth of described method separation tower (22); The top non-condensable gas outlet of described method separation tower (22) is connected through pipeline with the opening for feed of described membrane separation apparatus (28); The top liquid phase light fraction outlet of described method separation tower (22) is provided with branch outlet I and branch outlet J, branch outlet I is connected through pipeline with the upper feed inlet of described Methanol Wash Column (7), and branch outlet J is connected through pipeline with its top feed mouth of described NO recovery tower (13); The bottom liquid phases heavy constituent outlet of described method separation tower (22) is connected through pipeline with the underfeed mouth of described light constituent rectifying tower (23); The top light fraction outlet of described light constituent rectifying tower (23) is connected through pipeline with out-of-bounds alcohol retrieving arrangement; The bottom heavy constituent outlet of described light constituent rectifying tower (23) is connected through pipeline with the underfeed mouth of described ethylene glycol product tower (24); The top exit of described ethylene glycol product tower (24) and out-of-bounds 1,2-butyleneglycol recycling and processing device connect through pipeline; The outlet at bottom of described ethylene glycol product tower (24) is connected through pipeline with out-of-bounds recycling and processing device; The upper outlet of described ethylene glycol product tower (24) is ethylene glycol product outlet; Row's bleeder holes of described membrane separation apparatus (28) is connected through pipeline with out-of-bounds retrieving arrangement, and the recovery gas outlet of described membrane separation apparatus (28) is connected through pipeline with its top feed mouth of described hydrogenator (17).
2. a kind of commercial syngas mesohigh carbonylation as claimed in claim 1 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, and it is characterized in that, described oxonation device (1) is externally connected with dehydration tower (10); Described dehydration tower (10) is provided with opening for feed and dry gas outlet; The top exit of described esterification reaction tower (9) is connected through pipeline with the opening for feed of described dehydration tower (10) with the recovery gas outlet of described pressure-variable adsorption tank (16); The dry gas outlet of described dehydration tower (10) is connected through pipeline with described oxonation device (1) its top feed mouth.
3. a kind of commercial syngas mesohigh carbonylation as claimed in claim 2 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, described dehydration tower is made up of the mole sieve drier A of two alternate runs and regeneration and mole sieve drier B; Filled with adsorbent in mole sieve drier A and mole sieve drier B.
4. a kind of commercial syngas mesohigh carbonylation as claimed in claim 2 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, the bottom discharge mouth of described oxonation device (1) is connected with outlet heat exchanger I (3); Described outlet heat exchanger I (3) is provided with cold logistics import, cold stream outlet, thermal material import and hot stream outlet; Described CO feed conduit, N 2the dry gas outlet of feed conduit and dehydration tower (10) is connected through pipeline with the cold logistics import of described outlet heat exchanger I (3); The cold stream outlet of described outlet heat exchanger I (3) is connected through pipeline with its top feed mouth of described oxonation device (1); The bottom discharge mouth of described oxonation device (1) is connected through pipeline with the hot logistics import of described outlet heat exchanger I (3); The hot stream outlet of described outlet heat exchanger I (3) is connected through pipeline with the opening for feed of described first gas-liquid separator (4).
5. a kind of commercial syngas mesohigh carbonylation as claimed in claim 4 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, and it is characterized in that, described oxonation device (1) is externally connected with drum I (2); Described drum I (2) is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum I (2) is connected through pipeline with refrigerant feed conduit; The refrigerant exit of described drum I (2) is connected through pipeline with the bottom refrigerant import of described oxonation device (1); The top refrigerant exit of described oxonation device (1) is connected through pipeline with the liquid-vapor mixture import of described drum I (2); The vapour outlet of described drum I (2) is connected through pipeline with out-of-bounds vapor-recovery system.
6. a kind of commercial syngas mesohigh carbonylation as claimed in claim 5 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, between the branch outlet A of described Methanol Wash Column (7) and the underfeed mouth of described esterification reaction tower (9), be connected with carbonylation recycle compressor (8); Described carbonylation recycle compressor (8) is provided with import and outlet; Described branch outlet A is connected through pipeline with the import of described carbonylation recycle compressor (8); The outlet of described carbonylation recycle compressor (8) is connected through pipeline with the underfeed mouth of described esterification reaction tower (9).
7. a kind of commercial syngas mesohigh carbonylation as claimed in claim 6 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, the top exit of described NO recovery tower (13) and the bottom feed mouth of described methyl nitrite recovery tower (15) are connected with compressor (14); Described compressor (14) is provided with import and outlet; The top exit of described NO recovery tower (13) is connected through pipeline with the import of described compressor (14); The outlet of described compressor is connected through pipeline with the bottom feed mouth of described methyl nitrite recovery tower (15).
8. a kind of commercial syngas mesohigh carbonylation as claimed in claim 7 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, the bottom discharge mouth of described hydrogenator (17) is connected with outlet heat exchanger II (20); Described outlet heat exchanger II (20) is provided with cold logistics import, cold stream outlet, thermal material import and hot stream outlet; The recovery gas outlet of the outlet at bottom of described dimethyl oxalate rectifying tower (6), described membrane separation apparatus (28) and described in add Recycle hydrogen compressor (25) outlet be connected through pipeline with the cold logistics import of described outlet heat exchanger II (20); The cold stream outlet of described outlet heat exchanger II (20) is connected through pipeline with its top feed mouth of described hydrogenator (17); The bottom discharge mouth of described hydrogenator (17) is connected through pipeline with the hot logistics import of described outlet heat exchanger II (20); The hot stream outlet of described outlet heat exchanger II (20) is connected through pipeline with the opening for feed of described second gas-liquid separator.
9. a kind of commercial syngas mesohigh carbonylation as claimed in claim 8 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, its top feed mouth of described hydrogenator (17) is connected with the well heater that goes into operation (19); The described well heater that goes into operation (19) is provided with opening for feed and discharge port; The cold stream outlet of described outlet heat exchanger II (20) is connected through pipeline with the opening for feed of the described well heater that goes into operation (19); The discharge port of the described well heater that goes into operation is connected through pipeline with its top feed mouth of described hydrogenator (17).
10. a kind of commercial syngas mesohigh carbonylation as claimed in claim 9 produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, and it is characterized in that, described hydrogenator (17) is externally connected with drum II (18); Described drum II (18) is provided with refrigerant import, refrigerant exit, liquid-vapor mixture import and vapour outlet; The refrigerant import of described drum II (18) is connected through pipeline with refrigerant feed conduit; The refrigerant exit of described drum II (18) is connected through pipeline with the bottom refrigerant import of described hydrogenator (17); The top refrigerant exit of described hydrogenator (17) is connected through pipeline with the liquid-vapor mixture import of described drum II (18); The vapour outlet of described drum II (18) is connected through pipeline with out-of-bounds vapor-recovery system.
11. a kind of commercial syngas mesohigh carbonylations as claimed in claim 10 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, described second gas-liquid separator comprises high-pressure gas-liquid separator (21) and low-pressure gas-liquid separator (26); Described high-pressure gas-liquid separator (21) is provided with opening for feed, pneumatic outlet and liquid exit; Described low-pressure gas-liquid separator (26) is provided with opening for feed, pneumatic outlet and liquid exit; The bottom discharge mouth of described hydrogenator (17) is connected through pipeline with the opening for feed of described high-pressure gas-liquid separator (21); The pneumatic outlet of described high-pressure gas-liquid separator (21) is provided with branch outlet K and branch outlet L, branch outlet K is connected through pipeline with the described import adding Recycle hydrogen compressor (25), and branch outlet L is connected through pipeline with the opening for feed of described low-pressure gas-liquid separator (26); The liquid exit of described high-pressure gas-liquid separator (21) is connected through pipeline with the middle part opening for feed of described method separation tower (22); The pneumatic outlet of described low-pressure gas-liquid separator (26) is connected through pipeline with the opening for feed of described membrane separation apparatus (28); The liquid exit of described low-pressure gas-liquid separator (26) is connected through pipeline with the middle part opening for feed of described method separation tower (22).
12. a kind of commercial syngas mesohigh carbonylations as claimed in claim 11 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, before the opening for feed of described membrane separation apparatus (28), be provided with methanol absorption tank (27); Described methanol absorption tank (27) is provided with opening for feed and clean gas outlet; The pneumatic outlet of described low-pressure gas-liquid separator (26) is connected through pipeline with the opening for feed of described methanol absorption tank (27) with the top non-condensable gas outlet of described method separation tower (22); The clean gas outlet of described methanol absorption tank (27) is connected through pipeline with the opening for feed of described membrane separation apparatus (28).
13. a kind of commercial syngas mesohigh carbonylations as claimed in claim 1 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, described oxonation device (1) is plate-type reactor, tubular reactor or tubular type-board-like compound reactor.
14. a kind of commercial syngas mesohigh carbonylations as claimed in claim 13 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, and it is characterized in that, described oxonation device (1) is board-like fixed bed oxonation device; The center of described board-like fixed bed oxonation device is provided with plate groups lock chamber, and be provided with plate groups in described plate groups lock chamber, described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber to board-like fixed bed oxonation device inwall between be provided with beds; Be filled with oxonation catalyzer in beds, described beds is also provided with top entry and outlet at bottom; In the bottom of described board-like fixed bed oxonation device, the bottom refrigerant import of described board-like fixed bed oxonation device is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed oxonation device; At the top of described board-like fixed bed oxonation device, the its top feed mouth of described board-like fixed bed oxonation device is connected through pipeline with the top entry of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed oxonation device.
15. a kind of commercial syngas mesohigh carbonylations as claimed in claim 1 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, described esterification reaction tower (9) is packing tower or the column plate-filler mixing column simultaneously with deck portion and filler filling part.
16. a kind of commercial syngas mesohigh carbonylations as claimed in claim 1 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, described Methanol Wash Column (7), methanol rectifying tower (5), methanol distillation column (11), NO recovery tower (13), methyl nitrite recovery tower (15), dimethyl oxalate rectifying tower (6) and nitric acid concentration tower (12) they are packing tower, tray column or bubble-plate column.
17. a kind of commercial syngas mesohigh carbonylations as claimed in claim 1 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, described hydrogenator (17) is plate bed reactor, tubular reactor or board-like-tubular type combined reactor.
18. a kind of commercial syngas mesohigh carbonylations as claimed in claim 17 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, and it is characterized in that, described hydrogenator (17) is board-like fixed bed hydrogenation reactor; The center of described board-like fixed bed hydrogenation reactor is provided with plate groups lock chamber, is provided with plate groups in described plate groups lock chamber, and described plate groups lock chamber is also provided with bottom inlet and top exit; The outer wall of described plate groups lock chamber to board-like fixed bed hydrogenation reactor inwall between be provided with beds; Be filled with catalyst for hydrogenation in described beds, described beds is also provided with top entry and outlet at bottom; In the bottom of described board-like fixed bed hydrogenation reactor, the bottom refrigerant import of described board-like fixed bed hydrogenation reactor is connected through pipeline with the bottom inlet of described plate groups lock chamber, and the outlet at bottom of described beds is connected through pipeline with the bottom discharge mouth of described board-like fixed bed hydrogenation reactor; At the top of described board-like fixed bed hydrogenation reactor, the its top feed mouth of described board-like fixed bed hydrogenation reactor is connected through pipeline with the top entry of described beds, and the top exit of described plate groups lock chamber is connected through pipeline with the top refrigerant exit of described board-like fixed bed hydrogenation reactor.
19. a kind of commercial syngas mesohigh carbonylations as claimed in claim 1 produce dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol, it is characterized in that, described membrane separation apparatus (28) is in parallel or be connected in series and form by 1 ~ 100 hollow fiber film assembly.
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