CN109516902B - DMMn production equipment and method - Google Patents
DMMn production equipment and method Download PDFInfo
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- CN109516902B CN109516902B CN201910052686.1A CN201910052686A CN109516902B CN 109516902 B CN109516902 B CN 109516902B CN 201910052686 A CN201910052686 A CN 201910052686A CN 109516902 B CN109516902 B CN 109516902B
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Abstract
The invention relates to the field of fine chemical industry of conversion from coal chemical industry to petrochemical industry, in particular to DMMn production equipment and a DMMn production method. The DMMn production equipment comprises a primary flash evaporation system, an alkaline washing system and a crude DMMn rectification system, wherein the primary flash evaporation system comprises a flash evaporation tank and a flash evaporation discharging cooler; the alkaline washing system comprises a feeding mixer, an alkaline washing tank, a tank receiving tank at the top of the alkaline washing tank, a coalescer and a waste alkaline liquid tank, and the rectifying system comprises a rectifying tower 1 and a rectifying tower 2. The beneficial effects of the invention are as follows: effectively remove water, improve the product quality, operate steadily, save energy and protect environment.
Description
Field of the art
The invention relates to the field of fine chemical industry of conversion from coal chemical industry to petrochemical industry, in particular to DMMn production equipment and a DMMn production method.
(II) background art
The alcohol ether fuel test device of the Chinese safety chemical industry Co., ltd is mainly used for producing alcohol ether fuel (DMMn) products, and can also produce byproducts such as methylal, trioxymethylene and the like, wherein the design capacity is 5 ten thousand tons/year, and the operation elasticity is 70-110%. The device mainly comprises a formaldehyde preparation unit, a methylal preparation unit, a trioxymethylene synthesis unit and an alcohol ether fuel synthesis unit.
The formaldehyde preparation unit takes methanol as a raw material to produce formaldehyde. The methanol and oxygen are dehydrogenated and oxidized at 650 ℃ under the condition of silver catalyst to generate formaldehyde mixed gas, and then absorbed to generate formaldehyde solution with high concentration.
The methylal unit takes methanol and formaldehyde as raw materials, and under the action of a solid acid catalyst, methylal is synthesized through addition and dehydration, and then the methylal product with high concentration is obtained through procedures such as flash evaporation, rectification and the like.
The trioxymethylene synthesis unit takes formaldehyde produced by the formaldehyde production unit as a raw material, and performs TOX synthesis reaction under the action of an ionic liquid catalyst to generate TOX reaction gas, wherein the TOX concentration in the generated TOX reaction gas is low because the synthesis reaction is an equilibrium reaction, and the reaction gas is subjected to a series of refining processes such as concentration, extraction, alkali washing, water washing, separation with an extractant and the like to finally obtain a high-concentration trioxymethylene product.
The alcohol ether fuel synthesis unit takes methylal and trioxymethylene as raw materials, adopts a novel solid catalyst newly developed by the national institute of chemical and physical science of China to react at a certain temperature and under a certain pressure to generate alcohol ether fuel, and then carries out operations such as separation from reactants, deacidification, light component recovery and the like to obtain a high-purity alcohol ether fuel product.
Alcohol ether fuels are a generic term for a class of substances, the shorthand of which can be expressed as: CH (CH) 3 O(CH 2 O)nCH 3 (n is an integer greater than or equal to 1), wherein the range of n values with application meaning is: n is more than or equal to 1 and less than or equal to 8. Two alcohol ether products produced in alcohol ether workshop are DMM respectively 2 And DMMn, wherein DMM 2 Annual production 20132 tons and annual DMMn production 29940 tons.
(III) summary of the invention
The invention provides DMMn production equipment and method for improving the product purity, protecting environment and saving energy in order to make up the defects of the prior art.
The invention is realized by the following technical scheme:
the DMMn production equipment comprises a primary flash evaporation system, an alkaline washing system and a crude DMMn rectification system, wherein the primary flash evaporation system comprises a flash evaporation tank and a flash evaporation discharge cooler; the alkaline washing system comprises a feeding mixer, an alkaline washing tank, a tank receiving tank at the top of the alkaline washing tank, a coalescer and a waste alkaline liquid tank, and the rectifying system comprises a rectifying tower 1 and a rectifying tower 2.
The feeding mixer is arranged before the alkaline washing tank in the alkaline washing system, the alkaline washing tank is arranged between the feeding mixer and the alkaline washing tank top liquid receiving tank, the alkaline washing tank top liquid receiving tank is arranged between the alkaline washing tank and the waste alkali liquid tank, the coalescer is arranged between the alkaline washing tank and the alkaline washing tank top liquid receiving tank, and the waste alkali liquid tank is arranged behind the alkaline washing tank top liquid receiving tank.
The alkaline washing tank bottom discharge is divided into two paths, one path is connected with a branch port of an alkaline feed mixer, the other path is connected with a waste alkaline liquid tank, the branch port of the alkaline feed mixer is connected with an alkaline supplementing line, the alkaline washing tank top discharge is connected with a coalescer, and the coalescer is connected with an alkaline washing tank top liquid receiving tank.
The alkaline washing top liquid receiving tank is connected with the waste alkali liquid tank through a water drum, the alkaline washing top liquid receiving tank bottom discharging is connected with the rectifying tower, an alkaline washing tank circulating discharging pump is arranged between the alkaline washing tank and the waste alkali liquid tank, and the alkaline washing top liquid receiving tank is connected with the alkaline washing top liquid receiving tank discharging pump below the alkaline washing top liquid receiving tank.
The rectification 1 tower is arranged between an alkaline washing tank top liquid receiving tank and a rectification 2 tower, the feeding of the rectification 1 tower is connected with the discharging of the alkaline washing tank top liquid receiving tank, the gas phase of the rectification 1 tower top is connected with the inlet of a condenser of the rectification 1 tower top, the outlet of the condenser of the rectification 1 tower top is connected with the liquid receiving tank of the rectification 1 tower top, the discharging of the rectification 1 tower bottom is connected with the rectification 2 tower, the discharging of the liquid receiving tank of the rectification 1 tower top is connected with the raw material recovery, and a liquid receiving tank discharging pump of the rectification 1 tower top is arranged below the liquid receiving tank of the rectification 1 tower top.
The feed inlet of the rectifying tower 2 is connected with the discharge pump at the bottom of the rectifying tower 1, the gas phase at the top of the rectifying tower 2 is connected with the inlet of the condenser at the top of the rectifying tower 2, the outlet of the condenser at the top of the rectifying tower 2 is connected with the liquid receiving tank at the top of the rectifying tower 2, the discharge of the liquid receiving tank at the top of the rectifying tower 2 is connected with the raw material recovery, the rectifying tower 2 is connected with the feed of the product tower, the discharge pump at the bottom of the rectifying tower 2 is arranged below the rectifying tower, the reflux pump of the rectifying tower 2 is arranged between the upper part of the rectifying tower 2 and the liquid receiving tank at the top of the rectifying tower 2, and the discharge pump at the bottom of the liquid receiving tank at the top of the rectifying tower 2 is arranged.
The flash tank is arranged after the reaction discharge, the flash discharge cooler is arranged between the flash tank and the feed mixer, the inlet of the flash tank feed and flash tank discharge cooler is connected through a flash tank discharge pump, and the outlet of the flash tank discharge cooler is connected with the alkaline washing tank feed mixer.
A method for producing DMMn, comprising the steps of:
(1) Flash evaporating materials from a reactor through a flash tank, allowing a top gas phase to enter a light component for recovery, cooling a bottom material to 40 ℃ through a flash tank discharge cooler after passing through a flash tank discharge pump, and then sending the material to an alkaline washing tank after passing through a feed mixer;
(2) Uniformly mixing the bottom discharge from the flash tank with alkali liquor in a certain proportion through a mixer, pumping the bottom waste alkali liquor to a waste alkali liquor tank through a waste alkali liquor circulation discharge pump, and dehydrating the top discharge to an alkaline washing tank top liquid receiving tank through a coalescer;
(3) After the materials in the liquid receiving tank at the top of the alkaline washing tank are settled, discharging water to a waste alkaline liquid tank through a water dividing bag, further removing water, and delivering the water-removed materials to a rectifying tower;
(4) The materials from the liquid receiving tank at the top of the alkaline washing tank are rectified by a rectifying tower 1, and DMM at the top is obtained 1 Recovering the methylal, removing the crude DMMn at the bottom of the methylal to a rectification 2 tower, and controlling the temperature of the tower bottom at 100 ℃;
(5) Feeding the discharged material from the tower bottom of the rectification 1 tower into a rectification 2 tower, and enabling DMM at the top to enter 1 Recovering the methylal, removing the crude alcohol ether at the bottom to a rear product tower for continuous separation and purification, and controlling the temperature of the tower bottom at 120 ℃.
The beneficial effects of the invention are as follows: the method can effectively remove about 2% of water contained in the reaction materials after alkaline washing and sedimentation, further improve the product quality, prolong the service life of the adsorbent of the subsequent system while preventing the water-containing materials from hydrolysis and deterioration in the process of the subsequent rectification system, and realize energy conservation and consumption reduction; the reactor discharge is neutralized by adding alkali, and simultaneously sedimentation and dehydration are carried out. In the process, the alkali liquor reacts with formaldehyde to generate formic acid and water, so that the generation of formaldehyde is reduced and inhibited. The method reduces the risk of blocking the pipeline caused by formaldehyde, and reduces the complexity of using solid alkali, so that the production operation is more stable, the product purity is higher, the property is more stable, and the method is more environment-friendly.
(IV) description of the drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a process unit according to the present invention;
in the figure, a flash tank 100, a flash tank discharge pump 101, a flash tank discharge cooler 102, a feed mixer 200, an alkaline wash tank 201, a waste lye circulation discharge pump 202, a coalescer 203, an alkaline wash tank top liquid receiving tank 204, a waste lye tank 205, an alkaline wash tank top liquid receiving tank discharge pump 206, a waste lye pump 207, a rectification 1 tower 300, a rectification 1 tower bottom discharge pump 301, a rectification 1 tower top condenser 302, a rectification 1 tower top liquid receiving tank 303, a rectification 1 tower top liquid receiving tank discharge pump 304, a rectification 2 tower 401, a rectification 2 tower bottom discharge pump 402, a rectification 2 tower top condenser 403, a rectification 2 tower top liquid receiving tank 404, a rectification 2 tower reflux pump 405 and a rectification 2 tower top discharge pump 406.
(fifth) detailed description of the invention
The drawings illustrate one embodiment of the invention. The DMMn production apparatus in this embodiment includes a primary flash system, an alkaline wash system, and a crude DMMn rectification system, the primary flash system including a flash tank 100, a flash discharge cooler 102; the caustic wash system comprises a feed mixer 200, a caustic wash tank 201, a caustic wash tank top liquid receiving tank 204, a coalescer 203 and a spent caustic tank 205, and the rectification system comprises a rectification 1 column 300 and a rectification 2 column 401.
In the alkaline washing system, a feed mixer 200 is arranged before an alkaline washing tank 201, the alkaline washing tank 201 is arranged between the feed mixer 200 and an alkaline washing tank top liquid receiving tank 204, the alkaline washing tank top liquid receiving tank 204 is arranged between the alkaline washing tank 201 and a waste alkali liquid tank 205, a coalescer 203 is arranged between the alkaline washing tank 201 and the alkaline washing tank top liquid receiving tank 204, and the waste alkali liquid tank 205 is arranged behind the alkaline washing tank top liquid receiving tank 204. The bottom discharge of the alkaline washing tank 201 is divided into two paths, one path is connected with a branch port of the feed mixer 200, the other path is connected with the waste alkali tank 205, the branch port of the feed mixer 200 is connected with an alkali supplementing line, the top discharge of the alkaline washing tank 201 is connected with a coalescer 203, and the coalescer 203 is connected with a liquid receiving tank 204 on the top of the alkaline washing tank. The water drum of the alkaline top liquid receiving tank 204 is connected with a waste lye tank 205, the bottom discharge of the alkaline top liquid receiving tank 204 is connected with a rectifying tower, a waste lye circulating discharge pump 202 is arranged between the alkaline top liquid receiving tank 201 and the waste lye tank 205, and an alkaline top liquid receiving tank discharge pump 206 is connected below the alkaline top liquid receiving tank 204.
The rectification 1 tower 300 is arranged between the alkaline washing tank top liquid receiving tank 204 and the rectification 2 tower 401, the feeding of the rectification 1 tower 300 is connected with the discharging of the alkaline washing tank top liquid receiving tank 204, the gas phase at the top of the rectification 1 tower 300 is connected with the inlet of the rectification 1 tower top condenser 302, the outlet of the rectification 1 tower top condenser 302 is connected with the rectification 1 tower top liquid receiving tank 303, the discharging of the rectification 1 tower 300 is connected with the rectification 2 tower 401, the discharging of the rectification 1 tower top liquid receiving tank 303 is connected with the raw material recovery, and a rectification 1 tower top liquid receiving tank discharging pump 304 is arranged below the rectification 1 tower top liquid receiving tank 303. The feed inlet of the rectification 2 tower 401 is connected with the discharge of the rectification 1 tower 300 tower kettle through a rectification 1 tower bottom discharge pump 301, the top gas phase of the rectification 2 tower 401 is connected with the inlet of a rectification 2 tower top condenser 403, the outlet of the rectification 2 tower top condenser 403 is connected with a rectification 2 tower top liquid receiving tank 404, the discharge of the rectification 2 tower top liquid receiving tank 404 is connected with raw material recovery, the rectification 2 tower 401 is connected with product tower feed, a rectification 2 tower kettle discharge pump 402 is arranged below the rectification 2 tower 401, a rectification 2 tower reflux pump 405 is arranged between the upper part of the rectification 2 tower 401 and the rectification 2 tower top liquid receiving tank 404, and a rectification 2 tower top discharge pump 406 is arranged below the rectification 2 tower top liquid receiving tank 404.
The flash tank 100 is arranged after the reaction discharge, the flash tank discharge cooler 102 is arranged between the flash tank 100 and the feed mixer 200, the inlet of the flash tank 100 and the inlet of the flash tank discharge cooler 102 are connected through the flash tank discharge pump 101, and the outlet of the flash tank discharge cooler 102 is connected with the alkaline wash tank feed mixer 200.
The method for producing DMMn in this example comprises the steps of:
(1) The material from the reactor (crude alcohol ether: DMM) 2-10 Formaldehyde, formic acid, water, DMM 1 And TOX) is flashed through flash drum 100, and the top gas phase (crude DMM 1 ) Light component recovery was entered, bottom material (crude alcohol ether: DMM (digital media management) 2-10 Formaldehyde, formic acid, water, DMM 1 And TOX) is cooled to 40 ℃ by a flash tank discharge cooler 102 after passing through a flash tank discharge pump 101, and then sent to an alkaline wash tank 201 after passing through a feed mixer 200;
(2) The bottom discharge from flash tank 100 (crude alcohol ether: DMM) 2-10 Formaldehyde, formic acid, water, DMM 1 And TOX) and the alkali liquor are uniformly mixed according to a certain proportion through a mixer, the bottom waste alkali liquor is sent to a waste alkali liquor tank 205 through a waste alkali liquor circulation discharging pump 202, and the top discharge (crude alcohol ether: DMM (digital media management) 2-10 Water, DMM 1 And TOX) is dewatered by coalescer 203 to the top of the caustic wash tankA liquid tank 204;
(3) The material in the tank 204 (crude alcohol ether: DMM) at the top of the alkaline washing tank 2-10 Water, DMM 1 And TOX) is settled and the water is removed further by draining the water in a ladle to a lye tank 205, the dehydrated material (crude alcohol ether: DMM) 2-10 Water, DMM 1 And TOX) to a rectifying column;
(4) The material from the caustic wash tank top receiver tank 204 (crude alcohol ether: DMM) 2-10 Water, DMM 1 And TOX) is rectified by a rectification 1 column 300, top DMM 1 Recovering the methylal, removing the crude DMMn at the bottom of the rectification 2 tower 401, and controlling the temperature of the bottom of the tower at 100 ℃;
(5) Discharging from the 300 tower bottom of the rectification 1 tower (crude alcohol ether: DMM) 2-10 Water, DMM 1 And TOX) into a rectification 2 column 401, top DMM 1 Recovery of the noracetal, bottom crude alcohol ether (DMM 2-10 And TOX) to the rear product tower for further separation and purification, and the bottom temperature is controlled at 120 ℃.
During operation, the pressure of the liquid level gauge of the flash tank 100 is closely paid attention to, overpressure is not needed, the outlet temperature of the discharging cooler is not suitable to be higher than 50 ℃, the feeding temperature of the alkaline washing tank 201 is not suitable to be higher than 50 ℃, a certain liquid level is established before the alkaline washing tank 201 is fed, alkali liquor circulation is started, alkali liquor is kept within a certain range after the alkali liquor is fed, low-concentration alkali is timely discharged, concentrated alkali is supplemented, when the pressure difference of a filter element of the coalescer 203 is larger than 0.1MPa, a standby coalescer is switched, the water division boundary is not higher than 50%, the separation effect of the rectification 1 tower 300 is required to be ensured, the temperature of the tower kettle of the rectification 1 tower 300 is controlled to be 100 ℃, and DMM in the rectification 2 tower 401 is ensured 1 The temperature of the bottom of the rectifying 2 column 401 is controlled to be 120 ℃.
By adopting the DMMn production equipment and the DMMn production method, about 2% of water contained in the reaction materials after alkaline washing and sedimentation can be effectively removed, the product quality is further improved, the service life of the adsorbent of the follow-up system is prolonged while the water-containing materials are prevented from being hydrolyzed and deteriorated in the follow-up rectification system process, and the energy conservation and consumption reduction are realized; the reactor discharge is neutralized by adding alkali, and simultaneously sedimentation and dehydration are carried out. In the process, the alkali liquor reacts with formaldehyde to generate formic acid and water, so that the generation of formaldehyde is reduced and inhibited. The method reduces the risk of blocking the pipeline caused by formaldehyde, and reduces the complexity of using solid alkali, so that the production operation is more stable, the product purity is higher, the property is more stable, and the method is more environment-friendly.
Claims (3)
1. A DMMn production facility comprising a primary flash system, an alkaline wash system, and a crude DMMn rectification system, the primary flash system comprising a flash tank (100), a flash discharge cooler (102); the alkali washing system comprises a feed mixer (200), an alkali washing tank (201), an alkali washing tank top liquid receiving tank (204), a coalescer (203) and a waste lye tank (205), the rectifying system comprises a rectifying 1 tower (300) and a rectifying 2 tower (401), the feed mixer (200) in the alkali washing system is arranged before the alkali washing tank (201), the alkali washing tank (201) is arranged between the feed mixer (200) and the alkali washing tank top liquid receiving tank (204), the alkali washing tank top liquid receiving tank (204) is arranged between the alkali washing tank (201) and the waste lye tank (205), the coalescer (203) is arranged between the alkali washing tank (201) and the alkali washing tank top liquid receiving tank (204), the waste lye tank (205) is arranged behind the alkali washing tank top liquid receiving tank (204), a water bag of the alkali washing tank top liquid receiving tank (204) is connected with the waste lye tank (205), the bottom of the alkali washing tank top liquid receiving tank (204) is connected with the rectifying tower, the alkali washing tank top liquid (205) is connected with a gas phase pump (301) of a liquid receiving tank (2) of a circulating pump (401) arranged between the alkali washing tank (201) and the rectifying 2, the liquid tank top liquid receiving tank top liquid (401) is connected with a liquid outlet (2) of the rectifying tank top liquid receiving tank (301) and a circulating pump (2, the liquid outlet (301) is arranged between the liquid tank top liquid tank (2) and the rectifying tank top liquid receiving tank (2) and the rectifying tank top liquid receiving the liquid tank top liquid receiving tank (2) and the liquid tank top liquid circulating the liquid tank (2) and the liquid tank top liquid tank (3), the outlet of a rectifying 2 tower top condenser (403) is connected with a rectifying 2 tower top liquid receiving tank (404), the discharging of the rectifying 2 tower top liquid receiving tank (404) is connected with raw material recovery, a rectifying 2 tower (401) is connected with product tower feeding, a rectifying 2 tower kettle discharging pump (402) is arranged below the rectifying 2 tower (401), a rectifying 2 tower reflux pump (405) is arranged between the rectifying 2 tower (401) and the rectifying 2 tower top liquid receiving tank (404), a rectifying 2 tower top discharging pump (406) is arranged below the rectifying 2 tower top liquid receiving tank (404), a flash tank (100) is arranged between the flash tank (100) and a feeding mixer (200), the feeding of the flash tank (100) is connected with the inlet of the flash tank discharging cooler (102) through the flash tank discharging pump (101), and the outlet of the flash tank discharging cooler (102) is connected with the alkaline washing tank feeding mixer (200);
the production method comprises the following steps:
(1) Flash evaporating materials from a reactor through a flash tank (100), allowing a top gas phase to enter a light component for recovery, cooling a bottom material to 40 ℃ through a flash tank discharge cooler (102) after passing through a flash tank discharge pump (101), and sending the bottom material to an alkaline washing tank (201) after passing through a feed mixer (200);
(2) Uniformly mixing bottom discharge from a flash tank (100) with alkali liquor according to a certain proportion through a mixer, conveying the bottom waste alkali liquor to a waste alkali liquor tank (205) through a waste alkali liquor circulation discharge pump (202), and dehydrating top discharge to an alkali wash tank top liquid receiving tank (204) through a coalescer (203);
(3) After the materials in the liquid receiving tank (204) at the top of the alkaline washing tank are settled, discharging water to a waste alkali liquid tank (205) through a water dividing bag, further removing the water, and delivering the water-removed materials to a rectifying tower;
(4) Rectifying the material from the liquid receiving tank (204) at the top of the alkaline washing tank by a rectifying tower 1 (300), recovering DMM 1 methylal at the top, removing crude DMMn at the bottom by a rectifying tower 2 (401), and controlling the temperature of the bottom of the tower at 100 ℃;
(5) And (3) discharging from the tower bottom of the rectification 1 tower (300) and feeding into the rectification 2 tower (401), recovering DMM 1 noracetal at the top, continuously separating and purifying crude alcohol ether at the bottom by a rear product tower, and controlling the tower bottom temperature at 120 ℃.
2. The DMMn production apparatus of claim 1, wherein: the bottom discharge of the alkaline washing tank (201) is divided into two paths, one path is connected with a branch port of the feeding mixer (200), the other path is connected with the waste alkali tank (205), the branch port of the feeding mixer (200) is connected with an alkali supplementing line, the top discharge of the alkaline washing tank (201) is connected with the coalescer (203), and the coalescer (203) is connected with the liquid receiving tank (204) at the top of the alkaline washing tank.
3. The DMMn production apparatus of claim 1, wherein: the rectification 1 tower (300) is arranged between an alkaline washing tank top liquid receiving tank (204) and a rectification 2 tower (401), the feeding of the rectification 1 tower (300) is connected with the discharging of the alkaline washing tank top liquid receiving tank (204), the gas phase at the top of the rectification 1 tower (300) is connected with the inlet of a rectification 1 tower top condenser (302), the outlet of the rectification 1 tower top condenser (302) is connected with a rectification 1 tower top liquid receiving tank (303), the discharging of the bottom of the rectification 1 tower (300) is connected with a rectification 2 tower (401), the discharging of the rectification 1 tower top liquid receiving tank (303) is connected with raw material recovery, and a rectification 1 tower top liquid receiving tank discharging pump (304) is arranged below the rectification 1 tower top liquid receiving tank (303).
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CN102701923A (en) * | 2012-06-11 | 2012-10-03 | 北京科尔帝美工程技术有限公司 | System device and process for preparing polymethoxy dimethyl ether |
CN202808649U (en) * | 2012-06-11 | 2013-03-20 | 北京科尔帝美工程技术有限公司 | Systemic device for preparing polyoxymethylene dimethyl ether |
CN204644230U (en) * | 2015-05-14 | 2015-09-16 | 江苏凯茂石化科技有限公司 | Formaldehyde absorption process unit in a kind of polymethoxy dimethyl ether synthesis |
CN107118083A (en) * | 2017-06-03 | 2017-09-01 | 天津大学 | A kind of apparatus and method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde |
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2019
- 2019-01-21 CN CN201910052686.1A patent/CN109516902B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102701923A (en) * | 2012-06-11 | 2012-10-03 | 北京科尔帝美工程技术有限公司 | System device and process for preparing polymethoxy dimethyl ether |
CN202808649U (en) * | 2012-06-11 | 2013-03-20 | 北京科尔帝美工程技术有限公司 | Systemic device for preparing polyoxymethylene dimethyl ether |
CN204644230U (en) * | 2015-05-14 | 2015-09-16 | 江苏凯茂石化科技有限公司 | Formaldehyde absorption process unit in a kind of polymethoxy dimethyl ether synthesis |
CN107118083A (en) * | 2017-06-03 | 2017-09-01 | 天津大学 | A kind of apparatus and method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde |
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