CN102001938A - Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid - Google Patents

Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid Download PDF

Info

Publication number
CN102001938A
CN102001938A CN2009101947578A CN200910194757A CN102001938A CN 102001938 A CN102001938 A CN 102001938A CN 2009101947578 A CN2009101947578 A CN 2009101947578A CN 200910194757 A CN200910194757 A CN 200910194757A CN 102001938 A CN102001938 A CN 102001938A
Authority
CN
China
Prior art keywords
oxalic acid
barkite
condenser
oxalate
esterifier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2009101947578A
Other languages
Chinese (zh)
Other versions
CN102001938B (en
Inventor
单文波
鲁文质
黄斌
徐长青
黄飚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Hua Yi derived energy chemical Co., Ltd
Original Assignee
Shanghai Coking Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Coking Co Ltd filed Critical Shanghai Coking Co Ltd
Priority to CN200910194757.8A priority Critical patent/CN102001938B/en
Publication of CN102001938A publication Critical patent/CN102001938A/en
Application granted granted Critical
Publication of CN102001938B publication Critical patent/CN102001938B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a process and a production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid. The method comprises the following steps of: reacting nitrogen oxide with alcohol in an esterification reactor to form nitrite, adding the nitrite into a gas phase coupling carbonylation reactor, and connecting the gas phase coupling carbonylation reactor with a condenser and an oxalate hydrolysis reactor. After being condensed by the condenser, outlet gas of the gas phase coupling carbonylation reactor is condensed into liquid-phase or solid-phase oxalate; the oxalate in the gas phase enters the oxalate hydrolysis reactor to generate the oxalic acid and the alcohol of corresponding ester; the ester solution of the corresponding ester can enter the subsequent esterification reactor for reaction; and the amount of the oxalate which enters the gas phase can be adjusted by adjusting the temperature of the condenser so as to adjust the distribution of the synthetic amount of the oxalate and the oxalic acid. Nitrogen oxide-containing noncondensable gas which passes through the oxalate hydrolysis reactor is recycled to enter the esterification reactor so as to realize the recycling of the nitrogen oxide. The process and the production system for synthesizing the dimethyl oxalate or the diethyl oxalate and coproducing the oxalic acid have low energy consumption and high productivity and meet the industrial requirement.

Description

The technology of a kind of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid and production system
Technical field
The present invention relates to the technology of a kind of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid, relate to a kind of carbon monoxide and oxygen technology in particular by nitrous acid ester synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid.
Background technology
Oxalic acid, dimethyl oxalate and oxalic acid diethyl ester all are important Organic Chemicals, oxalic acid extracts in the fields such as refining, metal treatment and cleaning and polymkeric substance be synthetic in chemosynthesis, pharmacy, rare earth element and is widely used, and dimethyl oxalate and oxalic acid diethyl ester low-voltage hydrogenation can make the generally attention that important industrial chemicals ethylene glycol is subjected to chemical field especially.
Traditional oxalic acid working system is sodium formate method, ethylene glycol oxidation, carbohydrate oxidation method etc., all because of seriously polluted or backward in technique, progressively is eliminated.The traditional working system of dimethyl oxalate and oxalic acid diethyl ester is to make by oxalic acid and alcohols esterification, because the backwardness of oxalic acid traditional method is subjected to the restriction of raw material, it is comparatively backward that technological line also seems.
In 1980, Japanese UBE company (EP0046598,1981; EP0086370,1983) and U.S. union carbide corporation (EP0057630,1982) successively disclosing with C0 is raw material, by means of methyl nitrite or ethyl nitrite, and be catalyzer with Pd/a-Al203, make CO oxidation coupling connection generate the method for dimethyl oxalate or the oxalic acid diethyl ester, (CN1054765A of Fujian Inst. of Matter Structure, Chinese Academy of Sciences simultaneously, 1991), University Of Tianjin (CN1149047,1997) and Shanghai Communications University (CN101190884) also disclose similar method.The reaction principle of this method is as follows: total reaction is: 2CO+2CH 3OH+1/2O 2→ (COOCH 3) 2+ H 2O (1)
Coupling connection carbonylation:
Figure B2009101947578D0000011
Esterification: 2CH 3OH+2NO+1/2O 2→ 2CH 3ONO+H 2O (1-2)
It is that raw material passes through methyl nitrite or ethyl nitrite that above-mentioned research and patent have been established with CO, at Pd/a-Al 2O 3Under the catalyzer, make the processing method of CO oxidation coupling connection generation dimethyl oxalate or oxalic acid diethyl ester, disclose the basic characteristics of such reaction, comprise support of the catalyst and activeconstituents, the basic technology condition of reaction etc.People (CN 85101616) such as Fujian Inst. of Matter Structure, Chinese Academy of Sciences good fortune Chen Geng Shen have also synthesized oxalic acid with similar method gas phase.But these methods all can not be implemented in the cover circulation device and produce dimethyl oxalate coproduction oxalic acid simultaneously or produce oxalic acid diethyl ester coproduction oxalic acid, and the product collection device of these methods all exists bigger technology shortcoming, limited its industrial applications, concrete shortcoming is as follows:
(CN 1056135 in University Of Tianjin, CN 101143821) middle reported method, be oxalic acid diethyl ester to be collected by condenser, its shortcoming is in order to guarantee the processing requirement of circulation gas, the oxalic acid diethyl ester of condenser during almost completely condensation oxonation device is worked off one's feeling vent one's spleen, make the condensation of condenser require very high, therefore need condenser under very low temperature, to move, and need bigger heat interchanging area, cause the condensation energy consumption to increase, the heat-exchange equipment investment increases, even condensing temperature is very low, heat interchanging area is also enough big, still the saturated vapo(u)r that has oxalic acid diethyl ester can enter hydrolysis in the follow-up esterifier like this in gas phase, cause problems such as equipment corrosion.For fear of the barkite hydrolysis equipment is caused corrosion, traditional method is to wash or ethanol mode such as wash is removed barkite in the gas phase by methyl alcohol, if methyl alcohol is washed the problems such as azeotropic that can cause byproduct methylcarbonate and methyl alcohol, ethanol is washed and can be occurred increasing unit equipment equally, increase problems such as separating energy consumption, can increase the product separation cost greatly.
Reported method in the Shanghai Jiaohua Co., Ltd (CN 101190884), be to wash the collection that tower carries out dimethyl oxalate by methyl alcohol, but this method is the physical absorption process, because the restriction of solubleness, need expend a large amount of methyl alcohol, and later separation barkite and methyl alcohol also needs a large amount of separation costs, and the by product methylcarbonate of dimethyl oxalate can form minimum azeotropic mixture with methyl alcohol, cause the separation difficulty when reclaiming methyl alcohol, separation costs is risen greatly.
Reported method in the Fujian Inst. of Matter Structure, Chinese Academy of Sciences (CN 1027257), be to carry out the collection of dimethyl oxalate by condensation methyl alcohol absorption tower, its shortcoming also is because the restriction of solubleness, need expend a large amount of methyl alcohol, and the by product methylcarbonate of dimethyl oxalate can form minimum azeotropic mixture with methyl alcohol, cause the separation difficulty when reclaiming methyl alcohol, separation costs is risen greatly, simultaneously because the condensation absorption, can cause than relatively large nitrous acid ester and be dissolved in the methanol solution of absorption tower still, because nitrous acid ester toxicity is bigger, when reclaiming methyl alcohol, must reclaim its desorb, further increased separation costs again.
People (CN85101616) such as Fujian Inst. of Matter Structure, Chinese Academy of Sciences good fortune Chen Geng Shen are though the gas phase synthesis method of disclosed catalytic synthesis of oxalic acid from carbon monoxide, coupling process can utilize the gas phase synthesis technique to produce high-quality oxalic acid, but because the oxalic acid market capacity is little, and the facility investment of gas phase synthesis method synthesis of oxalic acid is big, so limited its industrially scalable.
The CN1569800 patent disclosure of Shanghai Jiaohua Co., Ltd a kind of method and apparatus of oxalic acid coproduction Sodium Nitrite, this method can obtain the barkite product by esterification column and oxonation device, hydrolysis obtains oxalic acid then.But this patent introduction is a kind of one way route, and the NO that oxonation produces directly absorbs with alkali and obtains Sodium Nitrite, and NO can't recycle; Owing to adopt the one way route, unreacted carbon monoxide and the very difficult recycling of nitrous acid ester completely limited its technology and used during oxonation was worked off one's feeling vent one's spleen in addition.
Summary of the invention
The objective of the invention is to overcome with CO is that raw material passes through methyl nitrite or ethyl nitrite, under catalyst action, make the recycle system of CO oxidation coupling connection prepare energy consumption height in the technology of methyl oxalate or ethyl oxalate, separation costs increases and causes technical problem such as follow-up equipment corrosion, and the synthesizing dimethyl oxalate that a kind of suitable large-scale industrialization produces or the method for oxalic acid diethyl ester and the oxalic acid of coproduction simultaneously are provided.
The present invention introduces the equipment of condenser and barkite hydrolysis reactor in the CO gas phase coupling synthesis of oxalate circulation process of existing open report, solve many technical problems among the above-mentioned barkite preparation technology with this, and can realize the coproduction of barkite and oxalic acid.
The technology of synthesizing dimethyl oxalate of the present invention or oxalic acid diethyl ester and coproduction oxalic acid comprises the following steps:
1) will feed gas phase coupling connection oxonation device from the carbon monoxide that the gas mixture that contains methyl nitrite or ethyl nitrite and the benefit of esterifier are gone into and carry out coupling connection oxonation;
2) working off one's feeling vent one's spleen gas phase coupling connection oxonation device through after the condenser condenses, the barkite that is condensed into liquid phase or solid phase is discharged and collected through pipeline, will feed the alcohol that barkite hydrolysis reactor and water generation hydrolysis reaction generate oxalic acid and corresponding esters through the gas that contains barkite behind the condenser;
3) oxalic acid aqueous solution in the barkite hydrolysis reactor is discharged by the road and collected, the oxygen generation esterification that the mixed gas in the barkite hydrolysis reactor is gone into through esterifier and benefit generates methyl nitrite or ethyl nitrite;
4) will cycle back to through the mixed gas that contains methyl nitrite or ethyl nitrite that esterifier generates in the gas phase coupling connection oxonation device, repeating step 1-4 constitutes circulation, realizes the recycle of oxynitride, obtains barkite and coproduction oxalic acid.
Coupling connection oxonation in the described step 1 adopts conventional CO and methyl nitrite or ethyl nitrite coupling connection oxonation condition to carry out.As temperature is 120 ℃-150 ℃, and pressure range is 0.1MPa~0.5MPa, and catalyst body is Pd/a-Al 2O 3Deng.
Condenser in the described step 2 is provided with one or more.The temperature range of condenser is-20 ℃~90 ℃, and pressure range is 0.1MPa~0.5MPa.
The temperature range of described barkite hydrolysis reactor is 25 ℃~98 ℃, and pressure range is 0.1MPa~0.5MPa.
The barkite hydrolysis reactor can be a tower reactor, also can be tank reactor or the other types reactor that can realize its barkite hydrolysis reaction.
Described esterifier adopts conventional esterification condition to carry out.As temperature range is 25 ℃~55 ℃, and pressure range is 0.1MPa~0.5MPa.
Further, step 2 also comprises by the temperature in the regulation and control condenser, changes the ratio of final product barkite and oxalic acid.The temperature adjusting scope of condenser is-20 ℃~90 ℃, and temperature is low more, and the ratio of final product barkite and oxalic acid is high more, and the ratio modification scope of barkite and oxalic acid yield in unit time is weight ratio (0-648): 1, preferred (9-630): 1.The adding of this regulation and control step can be regulated and control the production capacity of barkite and oxalic acid flexibly according to the market requirement.
Further, step 3 for the mixed gas in the barkite hydrolysis reactor through enter after the condensation esterifier as reaction raw materials with mend the oxygen generation esterification of going into and generate methyl nitrite or ethyl nitrite.Concrete, mixed gas in the barkite hydrolysis reactor is through after the condensation, be separated into and do not coagulate circulation gas and aqueous alcoholic solution (being methanol solution or ethanolic soln), do not coagulate the bottom that enters esterifier after circulation gas and the oxygen that replenishes and NO mix, top by esterifier after aqueous alcoholic solution and the alcohol (methyl alcohol or ethanol) that replenishes mix enters, in esterifier, carry out esterification, produce methyl nitrite or ethyl nitrite.Condensation can realize by equipment such as condensers.Condensing temperature is-5 ℃-5 ℃.Esterification is a strong exothermal reaction, high temperature is unfavorable for reaction, thereby the pure liquid temp that this design can utilize the condenser appropriateness regulation and control behind the hydrolysis reactor to enter esterifier reduces the temperature of esterifier indirectly, and esterification is developed to favourable direction.
Further, in the step 4, after the compressed machine of the mixed gas that contains methyl nitrite or ethyl nitrite that esterifier generates boosts, cycle back in the gas phase coupling connection oxonation device.
Above-mentioned barkite is dimethyl oxalate or oxalic acid diethyl ester, and alcohol is methyl alcohol or ethanol.
The invention also discloses a kind of production system that is used for synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid technology, comprise gas phase coupling connection oxonation device, first condenser, barkite hydrolysis reactor and esterifier that circulation successively links to each other.
Concrete:
The air outlet of gas phase coupling connection oxonation device communicates through pipeline with the inlet mouth of first condenser;
First condenser also is provided with condensation product outlet and air outlet, and the air outlet of first condenser communicates through pipeline with the inlet mouth of barkite hydrolysis reactor;
The barkite hydrolysis reactor also is provided with water-in, liquid outlet and air outlet, and the air outlet of barkite hydrolysis reactor, oxygen blowdown pipe and benefit alcohol pipe (being used for replenishing methyl alcohol or ethanol) all communicate with the import of esterifier through pipeline;
Esterifier also is provided with liquid outlet and air outlet, and the air outlet of esterifier communicates through the inlet mouth of pipeline with gas phase coupling connection oxonation device with the carbon monoxide blowdown pipe.The pipeline that described esterifier air outlet communicates with the inlet mouth of gas phase coupling connection oxonation device is provided with and discharges a little, is used for speeding by a certain percentage to put circulation gas, to keep the balance of rare gas element ratio in the circulating system.
Preferable, described first condenser is provided with temperature control equipment, so that regulate the ratio of final product barkite and oxalic acid.
Preferable, be connected with second condenser between described barkite hydrolysis reactor and the esterifier, the air outlet of barkite hydrolysis reactor communicates with the inlet mouth of second condenser, the liquid returning tube road that second condenser is provided with condensation product outlet, air outlet and communicates with the barkite hydrolysis reactor, the condensation product outlet of second condenser communicates with the import on esterifier top after pipeline merges with mending pure pipe, and the air outlet of second condenser communicates with the import of esterifier bottom after pipeline merges with the oxygen blowdown pipe.
Preferable, the air outlet of described esterifier communicates with the inlet mouth of the 3rd condenser, the 3rd condenser is provided with phlegma liquid returning tube road and does not coagulate the circulation gas outlet, and phlegma all returns esterifier, does not coagulate to loop back coupling connection oxonation device after the compressed machine of circulation gas boosts.
Beneficial effect of the present invention:
The present invention increases the hydrolysis reactor of condenser and barkite on existing gas-phase synthesis of oxalate flow process or device, owing to be the barkite that utilizes in the hydrolysis reaction absorption circulation gas, belong to chemical absorption, so speed is fast, reactor is little with respect to the pure absorption tower scale of prior art; And because chemical absorption, impellent is big, and specific absorption is more thorough, solved in the circulation gas prior art since condensation thoroughly or because alcohol is washed not thorough, barkite enters the follow-up equipment hydrolysis by gas phase and causes equipment corrosion, energy consumption height, separation costs high-technology problem.
In addition, the present invention utilizes the raw material of the correspondent alcohol of hydrolysis reaction generation in the barkite hydrolysis reactor as esterifier, can also save the original amount that needs the use correspondent alcohol to enter.And the barkite hydrolysis reactor can be designed to the form of reactive distillation, promotes the efficient of hydrolysis reaction, can improve the concentration of correspondent alcohol at the reactive distillation cat head.
The present invention is also by condensation, most of barkite and carbonic ether are collected with liquid or solid-state form, reduced the separation costs of the barkite solution after the pure absorption, the trace carbon dimethyl phthalate behind the condenser in the circulation gas generates methyl alcohol and CO by hydrolysis reaction 2, avoided forming minimum azeotrope and formed with methyl alcohol, greatly reduce follow-up separating difficulty.
Totally compare existing gas-phase synthesis of oxalate technology, save energy consumption 10~30%.
In addition, in the technical problem of the present invention in solving former barkite synthesis technique, also realized the function of dimethyl oxalate or oxalic acid diethyl ester coproduction oxalic acid, only need the condensing temperature of simple adjustment condenser just can change the gas phase composition of circulation gas medium-height grass acid esters behind the condenser, can change the variant production production allocation of this device barkite and oxalic acid, thereby change the production capacity structure of product more flexibly according to market, make the economic interests maximization.The present invention compares independent oxalic acid preparation technology, has greatly reduced equipment cost especially, utilizes the equipment in the gas-phase synthesis of oxalate, and it is too high to have solved gas phase synthesis technique production oxalic acid cost, the problem of industrialization practical application difficulty.
Description of drawings
Fig. 1 realizes the production system synoptic diagram of technology of the present invention.
A is gas phase coupling connection oxonation device, and B is first condenser, and C is the barkite hydrolysis reactor, and D is an esterifier.
Embodiment
In conjunction with the accompanying drawings technology of the present invention is further described in detail: the present invention introduces first condenser and barkite hydrolysis reactor behind gas phase coupling connection oxonation device, parallel-series is in the circulation loop of oxonation device and esterifier.The temperature of coupling connection oxonation device is 120 ℃-150 ℃, and catalyst body is Pd/a-Al 2O 3, the temperature range of the first condenser B is-20 ℃~90 ℃, pressure range is 0.1MPa~0.5MPa; The temperature range of barkite hydrolysis reactor is 25 ℃~98 ℃, pressure range is 0.1MPa~0.5MPa, the temperature range of the condenser at barkite hydrolysis reactor top is-5 ℃~5 ℃, and the esterifier temperature range is 25 ℃~55 ℃, and pressure range is 0.1MPa~0.5MPa.
The following description of the implementation of this process:
Circulation gas and the CO that replenishes enter at device A gas phase coupling connection oxonation device top and begin reaction, and the coupling connection generates barkite and small amount of carbon acid esters; Reacted gas is through device A outlet at bottom pipeline 3 access arrangement B condensers, by changing the temperature of condenser, can change the amount of reaction gas medium-height grass acid esters and carbonic ether condensation, thereby can regulate the production capacity that generates barkite and oxalic acid, the barkite and the carbonic ether that are condensed into liquid form or solid form enter barkite product groove district in condenser bottom line 4, and uncooled barkite and carbonic ether gas phase are with the bottom of circulation gas access arrangement C barkite hydrolysis reactor, and the water counter current contact that enters with the hydrolysis reactor top, carry out the barkite hydrolysis reaction, generate the alcohol of oxalic acid and corresponding esters.The aqueous solution that contains oxalic acid enters follow-up oxalic acid crystallizer through the pipeline 7 bottom the equipment C and carries out following process, and circulation gas carries second condenser at the pure and mild gas phase water of gas phase access arrangement C barkite hydrolysis reactor top, is separated into not coagulate circulation gas and aqueous alcoholic solution.Do not coagulate and enter after the bottom of circulation gas access arrangement D esterifier and the oxygen that replenishes and NO mix, top by equipment D esterifier after aqueous alcoholic solution and the alcohol that replenishes mix enters, and in equipment D, carry out esterification, produce nitrous acid ester, the circulation gas that contains nitrous acid ester returns in the device A gas phase coupling connection oxonation device and reacts, and constitutes a complete circulation loop.This technology is compared conventional gas-phase synthesis of oxalate technology, saves energy consumption 10~30%.
The used production system of technology is as shown in Figure 1:
Comprise gas phase coupling connection oxonation device A, the first condenser B, barkite hydrolysis reactor C and esterifier D that circulation successively links to each other;
Wherein, the air outlet, bottom of gas phase coupling connection oxonation device A communicates through pipeline with the inlet mouth of the first condenser B;
First condenser is provided with temperature and pressure regulating device, and the first condenser B also is provided with condensation product outlet and air outlet, and the air outlet communicates through pipeline with the inlet mouth of barkite hydrolysis reactor C;
Barkite hydrolysis reactor C also is provided with water-in, liquid outlet and air outlet, and air outlet, oxygen blowdown pipe and benefit alcohol pipe (being used for replenishing methyl alcohol or ethanol) all communicate through the import of pipeline with esterifier D;
Further, be connected with second condenser between barkite hydrolysis reactor C and the esterifier D, the air outlet of barkite hydrolysis reactor communicates with the inlet mouth of second condenser, the liquid returning tube road that second condenser is provided with condensation product outlet, air outlet and communicates with the barkite hydrolysis reactor, the condensation product outlet communicates with the esterifier upper inlet after pipeline merges with mending pure pipe, and the air outlet communicates with the lower inlet of esterifier after pipeline merges with the oxygen blowdown pipe.
Esterifier D also is provided with liquid outlet and air outlet, and the air outlet of esterifier communicates through the inlet mouth of pipeline with gas phase coupling connection oxonation device A with the carbon monoxide blowdown pipe;
Further, the air outlet of described esterifier communicates with the inlet mouth of the 3rd condenser, the 3rd condenser is provided with phlegma liquid returning tube road and does not coagulate the circulation gas outlet, and phlegma all returns esterifier, does not coagulate to loop back coupling connection oxonation device after the compressed machine of circulation gas boosts.
The pipeline that the inlet mouth of the air outlet of esterifier D and gas phase coupling connection oxonation device communicates is provided with and discharges a little 13, is used for speeding by a certain percentage to put circulation gas, with the balance of rare gas element ratio in the maintenance circulating system.
Further set forth the present invention below in conjunction with embodiment, should be understood that example is not to be used to limit protection scope of the present invention.
Embodiment 1
Present embodiment is a flow process of dimethyl oxalate coproduction oxalic acid, and the pressure of all devices is 0.1MPa.The temperature of reaction of device A gas phase coupling connection oxonation device is 140 ℃, and catalyzer is Pd/a-Al 2O 3The technological temperature of equipment B condenser is 20 ℃, equipment C barkite hydrolysis reactor is designed to reaction fractionating tower in this example, reaction zone temperature is 85 ℃, the temperature of the condenser at barkite hydrolysis reactor top is-5 ℃, equipment D esterifier also is designed to reaction fractionating tower, and reaction zone temperature is 40 ℃.Following table is that present embodiment is formed according to each pipeline material of Figure of description 1, and 13 pipelines are for discharging a little in the accompanying drawing 1, and according to the circulating system processing requirement, the circulation gas of speeding by a certain percentage to put is to keep the balance of rare gas element ratio in the circulating system.After discharging, each material is formed and following table has fine difference.Present embodiment mesoxalic acid dimethyl ester output is 456Kg/h, coproduction oxalic acid 18.3Kg/h.The purity of the dimethyl oxalate that obtains through the equipment B condenser condenses is 98.3%, and handling back acquisition purity through rectifying or recrystallization is 99.9% dimethyl oxalate.
Figure B2009101947578D0000071
Figure B2009101947578D0000081
*: NO regulates magnitude of recruitment according to the circulation gas analysis
Embodiment 2
Present embodiment is a flow process of dimethyl oxalate coproduction oxalic acid, and the pressure of all devices is 0.1MPa.The temperature of reaction of device A gas phase coupling connection oxonation device is 140 ℃, and catalyzer is Pd/a-Al 2O 3The technological temperature of equipment B condenser is 40 ℃, equipment C barkite hydrolysis reactor is designed to reaction fractionating tower in the present embodiment, reaction zone temperature is 85 ℃, the temperature of the condenser at barkite hydrolysis reactor top is-5 ℃, equipment D esterifier also is designed to reaction fractionating tower, and reaction zone temperature is 40 ℃.Following table is that this example is formed according to each pipeline material of Figure of description 1.13 pipelines are for discharging a little in the accompanying drawing 1, and according to the circulating system processing requirement, the circulation gas of speeding by a certain percentage to put is to keep the balance of rare gas element ratio in the circulating system.After discharging, each material is formed and following table has fine difference.After not changing other processing condition and feed composition in the present embodiment and only changing the condenser technological temperature, dimethyl oxalate output is changed into 397Kg/h, coproduction oxalic acid 63Kg/h.
Figure B2009101947578D0000082
Figure B2009101947578D0000091
*: NO regulates magnitude of recruitment according to the circulation gas analysis
Embodiment 3
Except that the reaction zone temperature of equipment C barkite hydrolysis reactor is respectively 25 ℃, 98 ℃, all the other are identical with embodiment 1.The output of dimethyl oxalate and oxalic acid and embodiment 1 are approaching as a result, show that the hydrolysis reaction actuator temperature is less to the influence of production capacity.
Embodiment 4
Except that the pressure of all devices is the 0.5MPa, all the other are identical with embodiment 1.Dimethyl oxalate output: 475Kg/h, oxalic acid output: 3.8Kg/h.
Embodiment 5
Except that the temperature of condenser, all the other conditions are identical with embodiment 1, observe the adjusting of condenser temperature adjusting for dimethyl oxalate and oxalic acid output ratio with this, and the result is as shown in the table:
The temperature of condenser B -20℃ 30℃ 50℃ 90℃
Dimethyl oxalate 479Kg/h 431Kg/h 326Kg/h 0Kg/h
Oxalic acid 0.76Kg/h 37Kg/h 117Kg/h 366Kg/h
Embodiment 6
Present embodiment is a flow process of oxalic acid diethyl ester coproduction oxalic acid, and the pressure of all devices is 0.1MPa.The temperature of reaction of device A gas phase coupling connection oxonation device is 120 ℃, and catalyzer is Pd/a-Al 2O 3The technological temperature of equipment B condenser is 40 ℃, equipment C barkite hydrolysis reactor is designed to reaction fractionating tower in the present embodiment, reaction zone temperature is 85 ℃, the temperature of the condenser at barkite hydrolysis reactor top is-5 ℃, equipment D esterifier also is designed to reaction fractionating tower, and reaction zone temperature is 40 ℃.Following table is that this example is formed according to each pipeline material of Figure of description 1.13 pipelines are for discharging a little in the accompanying drawing 1, and according to the circulating system processing requirement, the circulation gas of speeding by a certain percentage to put is to keep the balance of rare gas element ratio in the circulating system.After discharging, each material is formed and following table has fine difference.After not changing other processing condition and feed composition in the present embodiment and only changing the condenser technological temperature, oxalic acid diethyl ester output is changed into 370Kg/h, coproduction oxalic acid 18.5Kg/h.
Figure B2009101947578D0000101
*: NO regulates magnitude of recruitment according to the circulation gas analysis
Embodiment 7
Except that the temperature of condenser, all the other conditions are identical with embodiment 6, observe the adjusting of condenser temperature adjusting for oxalic acid diethyl ester and oxalic acid output ratio with this, and the result is as shown in the table:
The temperature of condenser B -20℃ 30℃ 50℃ 90℃
Oxalic acid diethyl ester 399Kg/h 385Kg/h 341Kg/h 0Kg/h
Oxalic acid 0.616Kg/h 9.25Kg/h 36.37Kg/h 247Kg/h
Embodiment 8
Except that the reaction zone temperature of equipment C barkite hydrolysis reactor is respectively 25 ℃, 98 ℃, all the other are identical with embodiment 6.
The output of oxalic acid diethyl ester and oxalic acid and embodiment 6 are approaching as a result, show that the hydrolysis reaction actuator temperature is less to the influence of production capacity.
Embodiment 9
Except that the pressure of all devices is the 0.5MPa, all the other are identical with embodiment 1.Oxalic acid diethyl ester output: 395Kg/h, oxalic acid output 3Kg/h.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (10)

1. the technology of a synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid comprises the following steps:
1) will feed gas phase coupling connection oxonation device from the carbon monoxide that the gas mixture that contains methyl nitrite or ethyl nitrite and the benefit of esterifier are gone into and carry out coupling connection oxonation;
2) working off one's feeling vent one's spleen gas phase coupling connection oxonation device through after the condenser condenses, the barkite that is condensed into liquid phase or solid phase is discharged and collected through pipeline, will feed the alcohol that barkite hydrolysis reactor and water generation hydrolysis reaction generate oxalic acid and corresponding esters through the gas that contains barkite behind the condenser;
3) oxalic acid aqueous solution in the barkite hydrolysis reactor is discharged by the road and collected, the oxygen generation esterification that the mixed gas in the barkite hydrolysis reactor is gone into through esterifier and benefit generates methyl nitrite or ethyl nitrite;
4) will cycle back to through the mixed gas that contains methyl nitrite or ethyl nitrite that esterifier generates in the gas phase coupling connection oxonation device, repeating step 1-4 constitutes circulation, realizes the recycle of oxynitride, obtains barkite and coproduction oxalic acid.
2. the technology of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid according to claim 1, it is characterized in that, described step 2) condenser in is provided with one or more, and the temperature range of control condenser is-20 ℃~90 ℃, and pressure range is 0.1MPa~0.5MPa.
3. the technology of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid according to claim 1 is characterized in that the temperature controlling range of described barkite hydrolysis reactor is 25 ℃~98 ℃, and pressure control range is 0.1MPa~0.5MPa.
4. the technology of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid according to claim 1 is characterized in that, step 2 also comprises by the temperature in the regulation and control condenser, changes the ratio of final product barkite and oxalic acid.
5. as the technology of synthesizing dimethyl oxalate as described in the claim 4 or oxalic acid diethyl ester and coproduction oxalic acid, it is characterized in that, the temperature adjusting scope of described condenser is-20 ℃~90 ℃, and the ratio modification scope of barkite and oxalic acid yield in unit time is weight ratio (0-648): 1.
6. the technology of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid according to claim 1, it is characterized in that described step 3) is to enter oxygen generation esterification generation methyl nitrite or the ethyl nitrite that esterifier is gone into as reaction raw materials and benefit after the mixed gas in the barkite hydrolysis reactor passes through condensation.
7. the technology of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid according to claim 1, it is characterized in that, in the described step 4), after after the compressed machine of the mixed gas that contains methyl nitrite or ethyl nitrite that esterifier generates boosts, cycle back in the gas phase coupling connection oxonation device.
8. a production system that is used for synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid technology is characterized in that, comprises gas phase coupling connection oxonation device, first condenser, barkite hydrolysis reactor and esterifier that circulation successively links to each other.
9. as being used for the production system of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid technology as described in the claim 8, it is characterized in that the air outlet of gas phase coupling connection oxonation device communicates through pipeline with the inlet mouth of first condenser; First condenser also is provided with condensation product outlet and air outlet, and the air outlet of first condenser communicates through pipeline with the inlet mouth of barkite hydrolysis reactor; The barkite hydrolysis reactor also is provided with water-in, liquid outlet and air outlet, and the air outlet of barkite hydrolysis reactor, oxygen blowdown pipe and benefit alcohol pipe (being used for replenishing methyl alcohol or ethanol) all communicate with the import of esterifier through pipeline; Esterifier also is provided with liquid outlet and air outlet, and the air outlet of esterifier communicates through the inlet mouth of pipeline with gas phase coupling connection oxonation device with the carbon monoxide blowdown pipe.
10. as being used for the production system of synthesizing dimethyl oxalate or oxalic acid diethyl ester and coproduction oxalic acid technology as described in the arbitrary claim of claim 8-9, it is characterized in that described first condenser is provided with temperature control equipment.
CN200910194757.8A 2009-08-28 2009-08-28 Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid Active CN102001938B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910194757.8A CN102001938B (en) 2009-08-28 2009-08-28 Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910194757.8A CN102001938B (en) 2009-08-28 2009-08-28 Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid

Publications (2)

Publication Number Publication Date
CN102001938A true CN102001938A (en) 2011-04-06
CN102001938B CN102001938B (en) 2014-04-30

Family

ID=43809680

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910194757.8A Active CN102001938B (en) 2009-08-28 2009-08-28 Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid

Country Status (1)

Country Link
CN (1) CN102001938B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104892415A (en) * 2015-04-17 2015-09-09 中国科学院福建物质结构研究所 Material separation apparatus during dimethyl oxalate preparation process, and process method thereof
CN104892400A (en) * 2015-06-02 2015-09-09 福州大学 Intermittent reaction-continuous reaction rectification combined process for catalytic synthesis of oxalic acid
CN114887648A (en) * 2022-05-30 2022-08-12 中国石油大学(华东) Preparation method of catalyst for synthesizing dimethyl oxalate and co-producing dimethyl carbonate through carbonylation of methyl nitrite

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85101616A (en) * 1985-04-01 1986-08-13 中国科学院福建物质结构研究所 Catalytic synthesis of oxalic acid from carbon monoxide, coupling process
CN1054765A (en) * 1990-03-14 1991-09-25 中国科学院福建物质结构研究所 Continuous process for synthesizing oxalate by gas phase catalysis
CN1148589A (en) * 1995-10-20 1997-04-30 中国科学院福建物质结构研究所 Oxalate synthesis catalyst
CN1381310A (en) * 2002-05-09 2002-11-27 华东理工大学 Catalyst for gas-phase synthesis of oxalate and its preparing process
CN101143821A (en) * 2007-10-23 2008-03-19 天津大学 Method for preparing diethyl oxalate by coupling CO
CN101475473A (en) * 2008-12-18 2009-07-08 中国石油化工股份有限公司 Method for preparing oxalate by coupling reaction of CO
CN101475472A (en) * 2008-12-18 2009-07-08 中国石油化工股份有限公司 Method for preparing oxalate by coupling reaction of CO in gaseous phase

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85101616A (en) * 1985-04-01 1986-08-13 中国科学院福建物质结构研究所 Catalytic synthesis of oxalic acid from carbon monoxide, coupling process
CN1054765A (en) * 1990-03-14 1991-09-25 中国科学院福建物质结构研究所 Continuous process for synthesizing oxalate by gas phase catalysis
CN1148589A (en) * 1995-10-20 1997-04-30 中国科学院福建物质结构研究所 Oxalate synthesis catalyst
CN1381310A (en) * 2002-05-09 2002-11-27 华东理工大学 Catalyst for gas-phase synthesis of oxalate and its preparing process
CN101143821A (en) * 2007-10-23 2008-03-19 天津大学 Method for preparing diethyl oxalate by coupling CO
CN101475473A (en) * 2008-12-18 2009-07-08 中国石油化工股份有限公司 Method for preparing oxalate by coupling reaction of CO
CN101475472A (en) * 2008-12-18 2009-07-08 中国石油化工股份有限公司 Method for preparing oxalate by coupling reaction of CO in gaseous phase

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104892415A (en) * 2015-04-17 2015-09-09 中国科学院福建物质结构研究所 Material separation apparatus during dimethyl oxalate preparation process, and process method thereof
CN104892400A (en) * 2015-06-02 2015-09-09 福州大学 Intermittent reaction-continuous reaction rectification combined process for catalytic synthesis of oxalic acid
CN104892400B (en) * 2015-06-02 2016-09-07 福州大学 Catalyze and synthesize oxalic acid intermittent reaction and continuous reaction rectification group technology
CN114887648A (en) * 2022-05-30 2022-08-12 中国石油大学(华东) Preparation method of catalyst for synthesizing dimethyl oxalate and co-producing dimethyl carbonate through carbonylation of methyl nitrite
CN114887648B (en) * 2022-05-30 2023-08-04 中国石油大学(华东) Preparation method of catalyst for synthesizing dimethyl oxalate and co-producing dimethyl carbonate by methyl nitrite carbonylation

Also Published As

Publication number Publication date
CN102001938B (en) 2014-04-30

Similar Documents

Publication Publication Date Title
US20220410104A1 (en) Gas-liquid bubbling bed reactor, reaction system, and process for synthesizing carbonate ester
CN103130611B (en) Neopentyl glycol condensation hydrogenation production technique and device thereof
CN108997085B (en) Method and system for recovering by-products in dimethyl oxalate synthesis process
CN101367732A (en) Process and apparatus for preparing diethyl carbonate
CN111377802B (en) Preparation method and system of sec-butyl alcohol
CN101735182B (en) Process for continuously producing succinic anhydride through hydrogenation of maleic anhydride
CN103044257A (en) Alcoholysis method and device system for producing dioctyl terephthalate by polyester wastes
CN102795961B (en) Device and method for synthesizing sec-butyl alcohol by continuous reaction-rectification
CN110862301B (en) Sec-butyl alcohol refining method and device
CN114702375A (en) Separation system and method for ethanol-to-acetaldehyde product
CN102001938B (en) Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid
CN109748791B (en) Energy-saving method for producing dimethyl adipate
CN114315569A (en) Process for co-producing isopropanol and methyl acetate and production equipment thereof
CN109748790B (en) Method for producing dimethyl adipate
CN103588618A (en) Reactive distillation method and device for producing ethanol from methyl acetate by adding hydrogen
CN115160106A (en) Production device and method of sec-butyl alcohol
CN105693687B (en) High-efficiency reactive distillation method and device for glycol acetal/ketone reaction
CN107353206B (en) Production method and system of dimethyl carbonate with recyclable ester exchange catalyst
CN201567298U (en) Production system for synthesizing oxalic ester and co-producing oxalic acid
CN115253337A (en) Method and device for preparing isopropanol through two-tower thermal coupling reaction-variable pressure mixed rectification and application
CN115282913A (en) Reaction system and method for preparing methyl propionate
CN109646977B (en) Reactive distillation coupling tower and application thereof in preparation of formic acid
CN102952009B (en) Method, technology and production line for producing succinic acid and 1,4-butanediol by use of ethylene glycol
CN115672249B (en) System, method and application for preparing isopropyl ether through isopropanol etherification reaction rectification
CN104193619A (en) Technique for hydrogenation production of dimethyl succinate by using intermediate product of 1,4-butanediol device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee

Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD

Free format text: FORMER NAME: SHANGHAI COKING CO., LTD.

CP01 Change in the name or title of a patent holder

Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai

Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd

Address before: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai

Patentee before: Shanghai Coking Co., Ltd.