CN102001938B - 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 PDFInfo
- Publication number
- CN102001938B CN102001938B CN200910194757.8A CN200910194757A CN102001938B CN 102001938 B CN102001938 B CN 102001938B CN 200910194757 A CN200910194757 A CN 200910194757A CN 102001938 B CN102001938 B CN 102001938B
- Authority
- CN
- China
- Prior art keywords
- condenser
- oxalic acid
- barkite
- esterifier
- oxalate
- 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.)
- Active
Links
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
Technical field
The present invention relates to the technique of a kind of synthesizing dimethyl oxalate or oxalic acid diethyl ester coproduction oxalic acid, relate in particular a kind of carbon monoxide and oxygen by the technique of nitrous acid ester synthesizing dimethyl oxalate or oxalic acid diethyl ester coproduction oxalic acid.
Background technology
Oxalic acid, dimethyl oxalate and oxalic acid diethyl ester are all important Organic Chemicals, oxalic acid extracts in the fields such as refining, metal treatment and cleaning and polymkeric substance be synthetic and is widely used in chemosynthesis, pharmacy, rare earth element, and dimethyl oxalate and oxalic acid diethyl ester low-voltage hydrogenation can make important industrial chemicals ethylene glycol and be subject to especially the generally attention of chemical field.
Traditional oxalic acid working system is sodium formate method, ethylene glycol oxidation, oxidation of carbohydrate etc., all because of seriously polluted or backward in technique, is progressively eliminated.The traditional working system of dimethyl oxalate and oxalic acid diethyl ester is to make by oxalic acid and alcohols esterification, due to the backwardness of oxalic acid traditional method, is subject to the restriction of raw material, and it is comparatively backward that technological line also seems.
In 1980, Japanese UBE company (EP0046598,1981; EP0086370,1983) and the U.S. (EP0057630 of union carbide corporation, 1982) successively disclose take CO as raw material, by means of methyl nitrite or ethyl nitrite, and take Pd/a-Al2O3 as catalyzer, make CO oxidation be coupled the method for oxalic dimethyl ester or oxalic acid diethyl ester, (the 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 the method is as follows:
Total reaction is: 2CO+2CH
3oH+1/2O
2→ (COOCH
3)
2+ H
2o (1)
Be coupled carbonylation:
Esterification: 2CH
3oH+2NO+1/2O
2→ 2CH
3oNO+H
2o (1-2)
Above-mentioned research and patent have been established and take CO as raw material, have been passed through methyl nitrite or ethyl nitrite, at Pd/a-Al
2o
3under catalyzer, make CO be oxidized the processing method that is coupled oxalic dimethyl ester 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.The people (CN 85101616) such as the good fortune Chen Geng of Fujian Inst. of Matter Structure, Chinese Academy of Sciences Shen have also synthesized oxalic acid by similar method gas phase.But these methods all can not realize, in a set of circulation device, produce dimethyl oxalate coproduction oxalic acid simultaneously or produce oxalic acid diethyl ester coproduction oxalic acid, and the product collecting device of these methods all exists larger technique shortcoming, limited its industrial applications, concrete shortcoming is as follows:
(the CN 1056135 of University Of Tianjin, CN 101143821) the middle method of reporting, by condenser, oxalic acid diethyl ester to be collected, its shortcoming is the processing requirement in order to guarantee circulation gas, condenser is the oxalic acid diethyl ester of total condensation oxonation device in working off one's feeling vent one's spleen almost, make the condensation of condenser require very high, therefore need condenser at very low temperature, to move, and need larger heat interchanging area, cause condensation energy consumption to increase, heat-exchange equipment investment increases, even if condensing temperature is very low, heat interchanging area is also enough large, still have the saturated vapo(u)r of oxalic acid diethyl ester in gas phase, can enter in follow-up esterifier and be hydrolyzed like this, cause the problems such as equipment corrosion.For fear of barkite hydrolysis, equipment is caused to corrosion, traditional method is to wash or the ethanol mode such as wash is removed the barkite in gas phase by methyl alcohol, if washing, methyl alcohol can cause the problems such as the azeotropic of byproduct methylcarbonate and methyl alcohol, ethanol is washed and be there will be equally increase unit equipment, increase the problems such as separating energy consumption, can greatly increase product separation cost.
The method of report in Shanghai Jiaohua Co., Ltd (CN 101190884), by methyl alcohol, to wash tower to carry out the collection of dimethyl oxalate, but this method is physical absorption process, due to the restriction of solubleness, need to 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 with the formation of methanol minimum azeotropic mixture, cause the separation difficulty while reclaiming methyl alcohol, make separation costs greatly increase.
The method of report in Fujian Inst. of Matter Structure, Chinese Academy of Sciences (CN 1027257), to carry out the collection of dimethyl oxalate by condensation methyl alcohol absorption tower, its shortcoming is also the restriction due to solubleness, need to expend a large amount of methyl alcohol, and the by product methylcarbonate of dimethyl oxalate can with the formation of methanol minimum azeotropic mixture, cause the separation difficulty while reclaiming methyl alcohol, make separation costs greatly increase, simultaneously because condensation absorbs, can cause than relatively large nitrous acid ester and be dissolved in the methanol solution that absorbs tower reactor, because nitrous acid ester toxicity is larger, when reclaiming methyl alcohol, must reclaim its desorb, further increased again separation costs.
The people (CN85101616) such as the good fortune Chen Geng of Fujian Inst. of Matter Structure, Chinese Academy of Sciences Shen are although the gas phase synthesis method of disclosed catalytic synthesis of oxalic acid from carbon monoxide, coupling process can utilize gas phase synthesis technique to produce the oxalic acid of high-quality, but because oxalic acid market capacity is little, and the facility investment of gas phase synthesis method synthesis of oxalic acid is large, so limited its industrially scalable.
The CN1569800 patent of Shanghai Jiaohua Co., Ltd discloses a kind of method and apparatus of oxalic acid coproduction Sodium Nitrite, and the method can obtain barkite product by esterification column and oxonation device, and then hydrolysis obtains oxalic acid.But this patent Introduction is a kind of one way route, the NO that oxonation produces directly absorbs and obtains Sodium Nitrite with alkali, and NO cannot recycle; In addition owing to adopting one way route, oxonation work off one's feeling vent one's spleen middle unreacted completely carbon monoxide and nitrous acid ester be difficult to recycle, limited its technology application.
Summary of the invention
The object of the invention is to overcome and take CO as raw material, pass through methyl nitrite or ethyl nitrite, under catalyst action, making CO be oxidized the recycle system being coupled, to prepare in the technique of methyl oxalate or ethyl oxalate energy consumption high, separation costs increases and causes the technical problems such as follow-up equipment corrosion, the synthesizing dimethyl oxalate or the also method of the oxalic acid of coproduction simultaneously of oxalic acid diethyl ester that provide a kind of applicable large-scale industrialization to produce.
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, with this, solve the many technical problems in above-mentioned barkite preparation technology, and can realize the coproduction of barkite and oxalic acid.
The technique of synthesizing dimethyl oxalate of the present invention or oxalic acid diethyl ester coproduction oxalic acid, comprises the following steps:
1) gas mixture that contains methyl nitrite or ethyl nitrite from esterifier and the carbon monoxide that fills into being passed into gas phase is coupled oxonation device and is coupled oxonation;
2) gas phase is coupled to the working off one's feeling vent one's spleen after condenser condenses of oxonation device, the barkite that is condensed into liquid phase or solid phase is discharged and collected through pipeline, the gas that contains barkite is passed into the alcohol of barkite hydrolysis reactor and water generation hydrolysis reaction oxalic and corresponding esters after condenser;
3) oxalic acid aqueous solution in barkite hydrolysis reactor is discharged by the road and collected, the mixed gas in barkite hydrolysis reactor generates methyl nitrite or ethyl nitrite through esterifier and the oxygen generation esterification filling into;
4) mixed gas that contains methyl nitrite or ethyl nitrite generating through esterifier is cycled back to gas phase and be coupled in oxonation device, repeating step 1-4 forms circulation, realizes the recycle of oxynitride, obtains barkite coproduction oxalic acid.
The oxonation that is coupled in described step 1 adopts conventional CO and methyl nitrite or ethyl nitrite to be coupled oxonation condition to carry out.If temperature is 120 ℃-150 ℃, pressure range is 0.1MPa～0.5MPa, and catalyst body is Pd/a-Al
2o
3deng.
Condenser in 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.
Barkite hydrolysis reactor can be tower reactor, can be also tank reactor or the other types reactor that can realize its barkite hydrolysis reaction.
Described esterifier adopts conventional esterification condition to carry out.If temperature range is 25 ℃～55 ℃, pressure range is 0.1MPa～0.5MPa.
Further, step 2 also comprises by the temperature in regulation and control condenser, changes the ratio of final product barkite and oxalic acid.The temperature adjusting scope of condenser is-20 ℃～90 ℃, temperature is lower, the ratio of final product barkite and oxalic acid is higher, and the ratio modification scope of barkite and oxalic acid yield in unit time is weight ratio (0-648): 1, and preferably (9-630): 1.Adding of this regulation and control step, can, according to the market requirement, regulate and control flexibly the production capacity of barkite and oxalic acid.
Further, step 3 generates methyl nitrite or ethyl nitrite for the mixed gas in barkite hydrolysis reactor enters esterifier after condensation as reaction raw materials and the oxygen generation esterification filling into.Concrete, mixed gas in barkite hydrolysis reactor is after condensation, cannot not be separated into solidifyingly circulation gas and moisture alcoholic solution (being methanol solution or ethanolic soln), after mixing, solidifying circulation gas and supplementary oxygen and NO enter the bottom of esterifier, moisture alcoholic solution and supplementary alcohol (methyl alcohol or ethanol) are entered by the top of esterifier after mixing, 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 alcohol liquid temp that this design can utilize the condenser appropriateness regulation and control after hydrolysis reactor to enter esterifier reduces the temperature of esterifier indirectly, makes esterification to favourable future development.
Further, in step 4, the mixed gas that contains methyl nitrite or ethyl nitrite generating through esterifier, after compressor boosts, cycles back to gas phase and is coupled in 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 for the synthesis of dimethyl oxalate or oxalic acid diethyl ester coproduction oxalic acid technique, comprise that the connected gas phase that circulates is successively coupled oxonation device, the first condenser, barkite hydrolysis reactor and esterifier.
Concrete:
The air outlet that gas phase is coupled oxonation device communicates through pipeline with the inlet mouth of the first condenser;
The first condenser is also provided with condensation product outlet and air outlet, and the air outlet of the first condenser communicates through pipeline with the inlet mouth of barkite hydrolysis reactor;
Barkite hydrolysis reactor is also provided with water-in, liquid outlet and air outlet, and air outlet, oxygen blowdown pipe and the benefit alcohol pipe (for supplementing methyl alcohol or ethanol) of barkite hydrolysis reactor all communicate with the import of esterifier through pipeline;
Esterifier is also provided with liquid outlet and air outlet, and the air outlet of esterifier communicates with the inlet mouth that carbon monoxide blowdown pipe is coupled oxonation device through pipeline and gas phase.Described esterifier air outlet and gas phase are coupled pipeline that the inlet mouth of oxonation device communicates and are provided with and discharge a little, for speeding by a certain percentage to put circulation gas, to keep the balance of rare gas element ratio in circulating system.
Preferably, described the first condenser is provided with temperature control equipment, so that regulate the ratio of final product barkite and oxalic acid.
Preferably, between described barkite hydrolysis reactor and esterifier, be connected with the second condenser, the air outlet of barkite hydrolysis reactor communicates with the inlet mouth of the second condenser, the liquid returning tube road that the second condenser is provided with condensation product outlet, air outlet and communicates with barkite hydrolysis reactor, the condensation product outlet of the second condenser communicates with the import on esterifier top after pipeline merges with mending alcohol pipe, and the air outlet of the second condenser communicates with the import of esterifier bottom after pipeline merges with oxygen blowdown pipe.
Preferably, 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 not solidifying circulation gas outlet, and phlegma all returns to esterifier, and not solidifying circulation gas loops back and is coupled oxonation device after compressor 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 being the barkite utilizing in hydrolysis reaction absorption cycle gas, belong to chemical absorption, therefore speed is fast, and reactor is little with respect to the alcohol absorption tower scale of prior art; And due to chemical absorption, impellent is large, and specific absorption is more thorough, has solved in circulation gas prior art because condensation is thoroughly or because alcohol wash is not thorough, barkite enters follow-up equipment hydrolysis by gas phase and causes equipment corrosion, energy consumption high, separation costs high-technology problem.
In addition, the present invention utilizes the correspondent alcohol of hydrolysis reaction generation in barkite hydrolysis reactor as the raw material of esterifier, can also save the amount that originally need to use correspondent alcohol to enter.And barkite hydrolysis reactor can be designed to the form of reactive distillation, the efficiency of facilitation of hydrolysis reaction, can improve the concentration of correspondent alcohol at reactive distillation tower top.
The present invention is also by condensation, most of barkite and carbonic ether are collected with liquid or solid-state form, the separation costs that has reduced the barkite solution after alcohol absorbs, the trace carbon dimethyl phthalate after condenser in circulation gas is by hydrolysis reaction methanol and CO
2, avoided and the formation of methanol minimum azeotrope composition, greatly reduce follow-up separating difficulty.
Totally compare existing gas-phase synthesis of oxalate technique, save energy consumption 10～30%.
In addition, the present invention is in the technical problem solving in 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 after condenser, can change the variant production production allocation of this device barkite and oxalic acid, thereby according to market, change more flexibly the production capacity structure of product, economic interests are maximized.The present invention compares independent oxalic acid preparation technology, has greatly reduced especially equipment cost, utilizes the equipment in gas-phase synthesis of oxalate, has solved gas phase synthesis technique and has produced oxalic acid high cost, the problem of industrialization practical application difficulty.
Accompanying drawing explanation
Fig. 1 realizes the production system schematic diagram of technique of the present invention.
A is that gas phase is coupled oxonation device, and B is the first condenser, and C is barkite hydrolysis reactor, and D is esterifier.
Embodiment
By reference to the accompanying drawings technique of the present invention is further described in detail: the present invention introduces the first condenser and barkite hydrolysis reactor after gas phase is coupled oxonation device, and parallel-series is in the circulation loop of oxonation device and esterifier.The temperature that is coupled 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 esterifier temperature range is 25 ℃～55 ℃, and pressure range is 0.1MPa～0.5MPa.
The implementation of this process is described as follows:
Circulation gas and supplementary CO are coupled oxonation device top in device A gas phase and enter and start reaction, are coupled oxalic ester and a small amount of carbonic ether, 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 of oxalic ester 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 entering with hydrolysis reactor top, carry out barkite hydrolysis reaction, the alcohol of oxalic and corresponding esters.Containing careless aqueous acid, through the pipeline 7 of equipment C bottom, enter follow-up oxalic acid crystallizer and carry out following process, and circulation gas carries second condenser at gas phase alcohol and gas phase water access arrangement C barkite hydrolysis reactor top, cannot not be separated into solidifyingly circulation gas and moisture alcoholic solution.After mixing, the bottom of solidifying circulation gas access arrangement D esterifier and supplementary oxygen and NO enter, moisture alcoholic solution and supplementary alcohol are entered by the top of equipment D esterifier after mixing, and in equipment D, carry out esterification, produce nitrous acid ester, the circulation gas that contains nitrous acid ester returns device A gas phase and is coupled in oxonation device and reacts, and forms a complete circulation loop.This technique is compared conventional gas-phase synthesis of oxalate technique, saves energy consumption 10～30%.
Technique production system used is as shown in Figure 1:
Comprise that the connected gas phase that circulates is successively coupled oxonation device A, the first condenser B, barkite hydrolysis reactor C and esterifier D;
Wherein, the air outlet, bottom that gas phase is coupled oxonation device A communicates through pipeline with the inlet mouth of the first condenser B;
The first condenser is provided with temperature and pressure regulating device, and the first condenser B is also provided with condensation product outlet and air outlet, and air outlet communicates through pipeline with the inlet mouth of barkite hydrolysis reactor C;
Barkite hydrolysis reactor C is also provided with water-in, liquid outlet and air outlet, and air outlet, oxygen blowdown pipe and benefit alcohol pipe (for supplementing methyl alcohol or ethanol) all communicate with the import of esterifier D through pipeline;
Further, between barkite hydrolysis reactor C and esterifier D, be connected with the second condenser, the air outlet of barkite hydrolysis reactor communicates with the inlet mouth of the second condenser, the liquid returning tube road that the second condenser is provided with condensation product outlet, air outlet and communicates with barkite hydrolysis reactor, condensation product outlet communicates with esterifier upper inlet after pipeline merges with mending alcohol pipe, and air outlet communicates with the lower inlet of esterifier after pipeline merges with oxygen blowdown pipe.
Esterifier D is also provided with liquid outlet and air outlet, and the air outlet of esterifier communicates with the inlet mouth that carbon monoxide blowdown pipe is coupled oxonation device A through pipeline and gas phase;
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 not solidifying circulation gas outlet, and phlegma all returns to esterifier, and not solidifying circulation gas loops back and is coupled oxonation device after compressor boosts.
The air outlet of esterifier D and gas phase are coupled pipeline that the inlet mouth of oxonation device communicates and are provided with and discharge a little 13, for speeding by a certain percentage to put circulation gas, to keep the balance of rare gas element ratio in circulating system.
Below in conjunction with embodiment, further set forth the present invention, should be understood that example is not for limiting the scope of the invention.
Embodiment 1
The 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 that device A gas phase is coupled 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 reactive distillation column in this example, reaction zone temperature is 85 ℃, the temperature of the condenser at barkite hydrolysis reactor top is-5 ℃, equipment D esterifier is also designed to reactive distillation column, and reaction zone temperature is 40 ℃.Following table is that the present embodiment forms according to each pipeline material of Figure of description 1, and in accompanying drawing 1,13 pipelines are for discharging a little, and according to circulating system processing requirement, the circulation gas of speeding by a certain percentage to put, to keep the balance of rare gas element ratio in circulating system.After discharging, each material composition has fine difference with following table.The present embodiment mesoxalic acid dimethyl ester output is 456Kg/h, coproduction oxalic acid 18.3Kg/h.The purity of dimethyl oxalate obtaining through equipment B condenser condenses is 98.3%, obtains purity and be 99.9% dimethyl oxalate after rectifying or recrystallization are processed.
| Nitrogen (Kg/h) | Nitrogen protoxide (Kg/h) | Carbon monoxide (Kg/h) | Methyl nitrite (Kg/h) | Carbonic acid gas (Kg/h) | Dimethyl oxalate (Kg/h) | Methylcarbonate (Kg/h) | Oxalic acid (Kg/h) | Methyl alcohol (Kg/h) | Oxygen (Kg/h) | Water (Kg/h) | |
| 1 | 2231 | 129 | 70 | 523 | |||||||
| 2 | 234 | ||||||||||
| 3 | 2231 | 386 | 70 | 480 | 20 | ||||||
| 4 | 456 | 8 | |||||||||
| 5 | 2231 | 386 | 70 | 24 | 12 | ||||||
| 6 | 90 | ||||||||||
| 7 | 18.3 | 74.9 |
| 8 | 21.5 | 5.4 | |||||||||
| 9 | 2231 | 386 | 70 | 5.9 | |||||||
| 10 | * | 69 | |||||||||
| 11 | 97.5 | 82.4 | |||||||||
| 12 | 350 |
*: NO regulates magnitude of recruitment according to circulation gas analysis
Embodiment 2
The 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 that device A gas phase is coupled 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 reactive distillation column in the present embodiment, reaction zone temperature is 85 ℃, the temperature of the condenser at barkite hydrolysis reactor top is-5 ℃, equipment D esterifier is also designed to reactive distillation column, and reaction zone temperature is 40 ℃.Following table is that this example is according to each pipeline material composition of Figure of description 1.In accompanying drawing 1,13 pipelines are for discharging a little, and according to circulating system processing requirement, the circulation gas of speeding by a certain percentage to put, to keep the balance of rare gas element ratio in circulating system.After discharging, each material composition has fine difference with following table.In the present embodiment, do not change other processing condition and feed composition and only change after condenser technological temperature, dimethyl oxalate output is changed into 397Kg/h, coproduction oxalic acid 63Kg/h.
| Nitrogen (Kg/h) | Nitrogen protoxide (Kg/h) | Carbon monoxide (Kg/h) | Methyl nitrite (Kg/h) | Carbonic acid gas (Kg/h) | Dimethyl oxalate (Kg/h) | Methylcarbonate (Kg/h) | Oxalic acid (Kg/h) | Methyl alcohol (Kg/h) | Oxygen (Kg/h) | Water (Kg/h) | |
| 1 | 2231 | 129 | 70 | 523 | |||||||
| 2 | 234 | ||||||||||
| 3 | 2231 | 386 | 70 | 480 | 20 | ||||||
| 4 | 397 | 3 | |||||||||
| 5 | 2231 | 386 | 70 | 83 | 17 | ||||||
| 6 | 90 | ||||||||||
| 7 | 63 | 47.6 | |||||||||
| 8 | 57.1 | 14 | |||||||||
| 9 | 2231 | 386 | 70 | 8.3 |
| 10 | * | 69 | |||||||||
| 11 | 133.1 | 91 | |||||||||
| 12 | 350 |
*: NO regulates magnitude of recruitment according to circulation gas analysis
Embodiment 3
Except 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 result dimethyl oxalate and oxalic acid and embodiment 1 approach, and show that hydrolysis reaction actuator temperature is less on the impact of production capacity.
Embodiment 4
Except the pressure of all devices is 0.5MPa, all the other are identical with embodiment 1.Dimethyl oxalate output: 475Kg/h, Oxalate Production: 3.8Kg/h.
Embodiment 5
Except the temperature of condenser, all the other conditions are identical with embodiment 1, observe condenser temperature regulate the adjusting for dimethyl oxalate and Oxalate Production ratio with this, and 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
The 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 that device A gas phase is coupled 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 reactive distillation column in the present embodiment, reaction zone temperature is 85 ℃, the temperature of the condenser at barkite hydrolysis reactor top is-5 ℃, equipment D esterifier is also designed to reactive distillation column, and reaction zone temperature is 40 ℃.Following table is that this example is according to each pipeline material composition of Figure of description 1.In accompanying drawing 1,13 pipelines are for discharging a little, and according to circulating system processing requirement, the circulation gas of speeding by a certain percentage to put, to keep the balance of rare gas element ratio in circulating system.After discharging, each material composition has fine difference with following table.In the present embodiment, do not change other processing condition and feed composition and only change after condenser technological temperature, oxalic acid diethyl ester output is changed into 370Kg/h, coproduction oxalic acid 18.5Kg/h.
| Nitrogen (Kg/h) | Nitrogen protoxide (Kg/h) | Carbon monoxide (Kg/h) | Ethyl nitrite (Kg/h) | Oxalic acid diethyl ester (Kg/h) | Oxalic acid (Kg/h) | Ethanol (Kg/h) | Oxygen (Kg/h) | Water (Kg/h) | |
| 1 | 2200 | 82 | 47 | 411 | |||||
| 2 | 153 | ||||||||
| 3 | 2200 | 246 | 47 | 400 | |||||
| 4 | 370 | ||||||||
| 5 | 2200 | 246 | 47 | 30 | |||||
| 6 | 60 | ||||||||
| 7 | 18.5 | 42.5 | |||||||
| 8 | 19 | 10 | |||||||
| 9 | 2200 | 246 | 47 | ||||||
| 10 | * | 44 | |||||||
| 11 | 230 | 59 | |||||||
| 12 | 463 |
*: NO regulates magnitude of recruitment according to circulation gas analysis
Embodiment 7
Except the temperature of condenser, all the other conditions are identical with embodiment 6, observe condenser temperature regulate the adjusting for oxalic acid diethyl ester and Oxalate Production ratio with this, and 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 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 result oxalic acid diethyl ester and oxalic acid and embodiment 6 approach, and show that hydrolysis reaction actuator temperature is less on the impact of production capacity.
Embodiment 9
Except the pressure of all devices is 0.5MPa, all the other are identical with embodiment 1.Oxalic acid diethyl ester output: 395Kg/h, Oxalate Production 3Kg/h.
Above said content is only 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 (4)
1. a technique for synthesizing dimethyl oxalate or oxalic acid diethyl ester coproduction oxalic acid, comprises the following steps:
1) gas mixture that contains methyl nitrite or ethyl nitrite from esterifier and the carbon monoxide that fills into being passed into gas phase is coupled oxonation device and is coupled oxonation;
2) gas phase is coupled to the working off one's feeling vent one's spleen after condenser condenses of oxonation device, the barkite that is condensed into liquid phase or solid phase is discharged and collected through pipeline, the gas that contains barkite is passed into the alcohol of barkite hydrolysis reactor and water generation hydrolysis reaction oxalic and corresponding esters after condenser; By the temperature in regulation and control condenser, change the ratio of final product barkite and oxalic acid;
3) oxalic acid aqueous solution in barkite hydrolysis reactor is discharged by the road and collected, mixed gas in barkite hydrolysis reactor is after condensation, cannot not be separated into solidifyingly circulation gas and moisture alcoholic solution, after mixing, solidifying circulation gas and supplementary oxygen and NO enter the bottom of esterifier, moisture alcoholic solution and supplementary alcohol are entered by the top of esterifier after mixing, in esterifier, carry out esterification, produce methyl nitrite or ethyl nitrite;
4) mixed gas that contains methyl nitrite or ethyl nitrite generating through esterifier is cycled back to gas phase and be coupled in oxonation device, repeating step 1-4 forms circulation, realizes the recycle of oxynitride, obtains barkite coproduction oxalic acid;
Described step 2) in condenser be provided with one or morely, controlling the temperature range of condenser is-20 ℃～90 ℃, pressure range is 0.1MPa～0.5MPa;
The temperature controlling range of described barkite hydrolysis reactor is 25 ℃～98 ℃, and pressure control range is 0.1MPa～0.5MPa.
2. the technique of synthesizing dimethyl oxalate or oxalic acid diethyl ester coproduction oxalic acid as claimed in claim 1, 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.
3. the technique of synthesizing dimethyl oxalate or oxalic acid diethyl ester coproduction oxalic acid as claimed in claim 1, it is characterized in that, in described step 4), the mixed gas that contains methyl nitrite or ethyl nitrite generating through esterifier, after compressor boosts, cycles back to gas phase and is coupled in oxonation device.
4. for the synthesis of a production system for dimethyl oxalate or oxalic acid diethyl ester coproduction oxalic acid technique, it is characterized in that, comprise that the connected gas phase that circulates is successively coupled oxonation device, the first condenser, barkite hydrolysis reactor and esterifier; The air outlet that gas phase is coupled oxonation device communicates through pipeline with the inlet mouth of the first condenser; The first condenser is also provided with condensation product outlet and air outlet, and the air outlet of the first condenser communicates through pipeline with the inlet mouth of barkite hydrolysis reactor; Described the first condenser is provided with temperature control equipment; Barkite hydrolysis reactor is also provided with water-in, liquid outlet and air outlet, and air outlet, oxygen blowdown pipe and the benefit alcohol Guan Junjing pipeline of barkite hydrolysis reactor communicate with the import of esterifier; Between described barkite hydrolysis reactor and esterifier, be connected with the second condenser, the air outlet of barkite hydrolysis reactor communicates with the inlet mouth of the second condenser, the liquid returning tube road that the second condenser is provided with condensation product outlet, air outlet and communicates with barkite hydrolysis reactor, the condensation product outlet of the second condenser communicates with the import on esterifier top after pipeline merges with mending alcohol pipe, and the air outlet of the second condenser communicates with the import of esterifier bottom after pipeline merges with oxygen blowdown pipe; Esterifier is also provided with liquid outlet and air outlet, and the air outlet of esterifier communicates with the inlet mouth that carbon monoxide blowdown pipe is coupled oxonation device through pipeline and gas phase.
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 CN102001938A (en) | 2011-04-06 |
| CN102001938B true 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) |
Families Citing this family (3)
| 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 |
| 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 |
| 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 |
Citations (7)
| 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 |
-
2009
- 2009-08-28 CN CN200910194757.8A patent/CN102001938B/en active Active
Patent Citations (7)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102001938A (en) | 2011-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20220410104A1 (en) | Gas-liquid bubbling bed reactor, reaction system, and process for synthesizing carbonate ester | |
| CN108997085A (en) | The recovery method and recovery system of by-product in a kind of dimethyl oxalate synthesis technology | |
| CN111377802B (en) | Preparation method and system of sec-butyl alcohol | |
| CN110862301B (en) | Sec-butyl alcohol refining method and device | |
| CN101830807B (en) | Synthesizing device and process for alkyl nitrite | |
| CN107082741A (en) | A kind of method of oxalate deep hydrogenation catalytic reaction synthesizing glycol | |
| CN109748791B (en) | Energy-saving method for producing dimethyl adipate | |
| CN109748790B (en) | Method for producing dimethyl adipate | |
| CN109748804B (en) | Production method of isopropanolamine | |
| CN102001938B (en) | Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid | |
| CN114702375A (en) | Separation system and method for ethanol-to-acetaldehyde product | |
| CN205347278U (en) | Synthetic methyl nitrite's device | |
| CN114315569A (en) | Process for co-producing isopropanol and methyl acetate and production equipment thereof | |
| CN220861410U (en) | Methyl chloride synthesis system without byproduct hydrochloric acid | |
| CN105693687B (en) | High-efficiency reactive distillation method and device for glycol acetal/ketone reaction | |
| CN101429099B (en) | Method for producing dichlorohydrin with glycerol | |
| CN115253337B (en) | Method, device and application for preparing isopropanol by two-tower thermal coupling reaction-pressure swing mixed rectification | |
| 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 | |
| CN101596394B (en) | Tail gas circle absorber in methylene reaction and distillation process and absoption method thereof | |
| CN212335079U (en) | Production process device for synthesizing methyl methacrylate by methyl acetate and formaldehyde | |
| CN102952009B (en) | Method, technology and production line for producing succinic acid and 1,4-butanediol by use of ethylene glycol | |
| CN109646977B (en) | Reactive distillation coupling tower and application thereof in preparation of formic acid | |
| 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. |