CN102659584A - Chemical reaction system for producing oxalic acid diester as main products by using sodium formate as raw materials - Google Patents
Chemical reaction system for producing oxalic acid diester as main products by using sodium formate as raw materials Download PDFInfo
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Abstract
The invention discloses a chemical reaction system for producing oxalic acid diester as main products by using sodium formate as raw materials. The chemical reaction system comprises a first reaction unit, a second reaction unit and a third reaction unit, wherein sodium formate is subjected to dehydrogenation reaction to generate sodium oxalate in the first reaction unit; in the second reaction unit, the sodium oxalate is mixed with solvents, then, the sulfuric acid is added, and the liquid and solid separation is carried out after the reaction, wherein the solid phase is sulfate, and the liquid phase contains rich oxalic acid diester; and in the third reaction unit, the liquid phase containing rich oxalic acid diester is subjected to distillation separation, then, the oxalic acid diester is respectively subjected to hydrolysis, hydrogenolysis and ammonolysis, and oxalic acid, alcohol, glycol and oxamide are obtained. The chemical reaction system has the advantages that the influence on environment is avoided, the environment problems of lead-containing sewage and other waste discharge do not exist, phosphates with higher additional value s re generated by sodium ions, the process separation becomes simple, the implementation is easy, and the production process reaches the requirements of clean production and energy saving environment-friendly type production process.
Description
Technical field
The present invention relates to the chemical reaction system, more particularly, relating to a kind of is the reactive system that raw material further carries out Chemical Manufacture with the sodium formiate.
Background technology
The technology utilization lead sulfate of China's synthesis method oxalic acid production makes precipitation agent and the sodium oxalate reaction generates lead oxalate deposition and metabisulfite solution, and liquid-solid clarification separates, and lead oxalate warp repeatedly rinsing is refining, and the rinsing liquid discharging causes the lead waste water contaminate environment.Lead oxalate adds sulfuric acid again and obtains oxalic acid and lead sulfate; Liquid-solid clarification separates the solid sulfur phase lead plumbate through repeatedly rinsing; Rinsing liquid, lead sulfate are got one ready and are recycled; Wherein sodium ion changes into the metabisulfite solution utilization and reclaims difficulty, and causes the environmental problem of leaded sewage, and this is contrary with saving with the environmental protection of current promotion undoubtedly.Therefore the production route of seeking a saving and environmental protection is the ten minutes urgent task.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; Provide one to be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate; Environment is not exerted an influence, more do not have the environmental problem of leaded sewage and other waste discharge, sodium ion generates the sodium sulfate of easy recovery; The technology separation becomes simple, and production technique reaches cleaner production and energy saving and environment friendly production technique.
The object of the invention is achieved through following technical proposals:
A kind of is that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate, comprises first reaction member, second reaction member and the 3rd reaction member, wherein:
In said first reaction member, sodium formiate generates sodium oxalate through dehydrogenation reaction;
In said second reaction member, with sodium oxalate and solvent, to wherein adding sulfuric acid, carry out liquid-solid separation after the reaction then, wherein solid phase is a sodium sulfate salt, is rich in oxalate diester in the liquid phase;
In said the 3rd reaction member, the liquid phase that is rich in oxalate diester is carried out fractionation by distillation, then to oxalate diester be hydrolyzed respectively, hydrogenolysis and ammonia separates, and obtains alcohol, oxalic acid, terepthaloyl moietie and oxamide.
In said first reaction member; Raw material is a sodium formiate: the production of sodium formiate utilizes the hot stove in ore deposit: the carbon monoxide of furnace of calcium carbide, tail gas of yellow phosphorus boiler through middle and high concentration pressurization, under the condition of heating with the alkaline reaction synthesising acid sodium; Be the carbon monoxide of China's invention fifties in last century, the method for caustic soda synthesising acid sodium in pipeline; Utilize the sodium formiate high-temperature dehydrogenation to change into sodium oxalate (referring to 2007 the 34th volume the 6th phases " experimental study of sodium formiate thermal decomposition behavior " of Beijing University of Chemical Technology's journal); But solubilizing agent wiring solution-forming desulfuration acid acidifying, the pressed powder sodium oxalate can obtain its content with the potassium permanganate chemical analysis.
In said second reaction member; Dehydrogenation adds solvent after processing sodium oxalate in system; To obtain suspension-s, then suspension-s is put into reactor drum, again to wherein adding sulfuric acid; React below being warming up to the boiling point of solvent simultaneously, question response finishes the back and adopts rinsing or suction filtration method to separate.Specifically:
After sodium oxalate is processed in dehydrogenation; Also there are as yet the not sodium formiate of dehydrogenation and by product yellow soda ash in the whole reaction system; Adding solvent (selects alcohols as solvent; For example methyl alcohol, ethanol, propyl alcohol, butanols are to high carbon chain alcohol) dissolve and mix after obtain aaerosol solution (be sodium oxalate solution, wherein liquid phase is that alcoholic solvent, solid phase staple are sodium oxalate).Then sodium oxalate suspension-s is put into reactor drum,, be warming up to simultaneously below the boiling point of selective solvent and react (for example below methyl alcohol 64 degree to wherein adding sulfuric acid; Below ethanol 78 degree); The temperature of under solvent boiling point, selecting is high more, and the reaction times is long more, and reaction effect is good more; The general at least 4 hours reaction times, can be preferred 4-12 hours.
Select the sulfuric acid of adding very important; Can select directly to use oleum (sulphuric acid soln of sulphur trioxide); Perhaps add sulphur trioxide liquid and gas of dimethyl ether or diethyl ether gas; Making it earlier generate methyl-sulfate or ethyl sulfate in system's internal reaction moment just contacts with sodium oxalate system immediately and reacts; Consumption that can be through regulating both combines the sulphur trioxide pipeline transportation as using gas washing in SA production so that have methyl-sulfate or ethyl sulfate in the system hardly, makes reactive system safer; Also can directly drop into methyl-sulfate or ethyl sulfate.
It is following to adopt rinsing or method of pumping filtration to carry out liquid-solid separation after question response finishes
(1) rinsing: the reaction rear suspension liquid shifts out supernatant after long-time sedimentation; The surplus throw out of institute is with repeatedly (3～6 times) washing of solvent; The washings of each washing stores to be got one ready and recycles, and last washings is provided by the solution that the distillation oxalate diester returns.
(2) suction filtration: the reaction rear suspension liquid is through the airtight vacuum suction filtration; Equipment is vacuum filtration groove, airtight vacuum suction filtration rotary drum, and for the first time solid phase is advanced the formulated suspension still behind the suction filtration, is mixed with suspension-s by a last circulation filtrating and carries out waiting for the second time, for the third time again and filter; Liquid phase burring acid diesters distillation workshop section behind the suction filtration; Separate oxalate diester and solution, solution is pumpback filter formulated suspension again, and each circulation preparation suction filtration all leaches the oxalate diester in the solid materials.
Reaction kettle having reflux exchanger, chuck interchanger, the stirring of vertical band injects sodium oxalate aaerosol solution and alcoholic solution, slowly puts into reaction kettle at the sulphur acid meter measuring tank that has function of measuring; Controlled temperature is in 25～200 ℃; Pressure keeps normal pressure, and system is airtight intact, and the reaction times was controlled at 8 hours; Reaction generation solid sediment sodium sulfate salt and liquid phase oxalate diester, oxalate compound solution; Come out liquid phase separation through airtight siphon, remove fractionation by distillation refined alcohol, oxalate diester, oxalic acid again, solid phase through repeatedly rinsing, siphon separate POV sodium solid.POV sodium solid leaves reaction kettle and in airtight negative pressure drying plant, steams slide, oven dry separation alcohol; Alcohol is got back to reaction kettle and is recycled; Airtight negative pressure bake out temperature about 200 ℃, pressure is that the sodium sulfate after the oven dry is packaged as finished product about Zhen idling Ya – 0.08MPa.
Get solid phase and confirm industrial anhydrous sodium sulfate content by the GB/T6009-2003 chemical examination: the anhydrous slufuric acid sodium content is more than 95%.Get the solid sulfur phase acid sodium-salt and adopt paraffin lake method infared spectrum to detect, shown in accompanying drawing 2, removing maybe be owing to the assorted peak of operation, and SODIUM SULPHATE ANHYDROUS 99PCT average peak area per-cent is 98.8%, proofreaies and correct through correction factor, and drawing the SODIUM SULPHATE ANHYDROUS 99PCT massfraction is 95.6%.The sample of " instance 1 " is taken from above-mentioned two kinds of detections.
In said the 3rd reaction member, the liquid phase (alcoholic solvent, micro-oxalic acid) that at first will be rich in oxalate diester carries out fractionation by distillation or low temperature crystallization separates, and it is following to carry out analyzing examples:
To the fractionation by distillation of oxalic acid diethyl ester, obtain liquid product at 184 ℃-186 ℃, add and send chromatographic instrument (the general sharp special science and technology limited Company PSP103-PSP103 type gas chromatograph in Jilin) after ethanol shakes all
The analytical results table
Annotate; Removing maybe be because the assorted peak that sample introduction needle is introduced, and oxalic acid diethyl ester average peak area per-cent is 88.81%, proofreaies and correct through correction factor, draws the oxalic acid diethyl ester massfraction and be 79.35%, the ethanol massfraction is near 20%
Also can obtain 184 ℃-186 ℃ liquid product in distillation utilizes HG/T 3272-2002 chemical examination to obtain the content of oxalic acid diethyl ester; Also can obtain flow process liquid product in distillation at 184 ℃～186 ℃; Adding water boils and concentrates cooling again at stink cupboard and obtain solid crystal and separate (the oxalic acid diethyl ester hydrolysis generates oxalic acid); Getting xln utilizes the GB1626-1988 chemical examination to obtain oxalic acid content, the anti-oxalic acid diethyl ester content that pushes away.Above-mentioned four kinds of methods detect get among the embodiment 4 sample chromatogram can be qualitative, quantitative amount of product is oxalic acid diethyl ester.
Low temperature crystallization to dimethyl oxalate separates: select to carry out the crystallisation by cooling suction filtration below 50 degrees centigrade and get the dimethyl oxalate crystal; Adding methyl alcohol shakes and all send chromatographic instrument (the general sharp special science and technology limited Company PSP103-PSP103 type gas chromatograph in Jilin), is made into the methanol solution that the dimethyl oxalate massfraction is 10wt%:
Also can get the dimethyl oxalate crystal by the crystallisation by cooling suction filtration, add water boil (hydrolysis of dimethyl oxalate) cooling and get crystallization and utilize the GB1626-1988 chemical examination obtaining the oxalic acid content after the hydrolysis, and then the anti-content of methyl oxalate that pushes away.The sample of embodiment 1 is taken from above-mentioned two kinds of detections, obtains the qualitative and quantitative analysis of dimethyl oxalate, and the dimethyl oxalate that obtains is purer.
Then the oxalate diester that obtains is developed respectively downstream be hydrolyzed, hydrogenolysis and ammonia separates; To obtain alcohol, oxalic acid, terepthaloyl moietie and oxamide; The alcohols material that wherein obtains can be circulated back in second reaction member and use; Wherein saidly be hydrolyzed to oxalate diester and water boils generation; Participate in Chinese invention patent " catalytic synthesis of oxalic acid from carbon monoxide, coupling process " and utilize oxalate diester hydrolysis under 80-110 ℃ of normal pressures (application number is 85101616, the applying date be that on April 1st, 1985, open day are on August 13rd, 1986); Said hydrogenolysis is oxalate diester hydrogenation synthesizing of ethylene glycol under the effect of catalyzer, and custom catalysts is copper chromium, copper chromium manganese, and temperature is that 210-220 degree centigrade of pressure is under the 2MPa; One tunnel gas phase (hydrogen); Hydrogenolysis is carried out in one tunnel liquid phase (oxalate diester) charging, referring to Chinese invention patent " a kind of oxalate diester nano catalyst for synthesizing glycol by hydrogenation " (application number is 200910111560.3, the applying date is on April 24th, 2009, be on October 27th, 2010 in open day), said ammonia separate for oxalate diester under normal pressure and ammonia carry out ammonia and separate synthetic oxamide.Hydrolysis, hydrogenolysis and ammonia for oxalate diester are separated, and existing chemical industry synthesis technique (temperature and pressure) and catalyzer thereof are selected all to discuss to some extent, can carry out respectively according to the character of oxalate diester, to obtain corresponding product.
In technical scheme of the present invention, the tail gas that at first utilizes the hot stove production in ore deposit to produce is produced sodium formiate, utilizes the sodium formiate high-temperature dehydrogenation to produce sodium oxalate then; Acidified again sodium oxalate aaerosol solution obtains oxalate diester, oxalate compound solution and sodium sulfate salt solid; Liquid-solid clarification separates, and solid phase is through repeatedly rinsing of solution, and rinsing liquid is got one ready and recycled; The solid sulfur phase acid sodium-salt is processed sodium sulfate salt through refining oven dry; Oxalate diester, oxalate compound solution through separate oxalate diester (dimethyl oxalate, oxalic acid diethyl ester), oxalic acid, add through refining that water generates oxalic acid, hydrogenation generates terepthaloyl moietie or ammonification generates oxamide, has following advantage:
(1) tail gas that utilizes the hot stove calcium carbide in ore deposit, phosphorus production to produce is produced sodium formiate; Make calcium carbide, phosphorus production not have exhaust emissions point day lamp problem of environment pollution caused; Technology reaches environmental protection, energy-conservation, cleaner production, and sodium formiate production utilizes the hot furnace exhaust gas in ore deposit to be rich in producing sodium formate from carbonic oxide, produces carbon monoxide than reducing gas compression energy consumption 2/3rds with coke, coal; Raw material preheating, work in-process evaporation oven dry consumption steam reduce by 2/3rds; Tail gas contains truncate burning boiler burning of inflammable gas (hydrogen) and produces steam or put forward its usefulness of hydrogen behind the synthesising acid sodium, does not have exhaust gas emission to influence environmental problem, makes sodium formiate production reach environmental protection, energy-conservation, cleaner production.
(2) sodium oxalate production utilizes the sodium formiate high-temperature dehydrogenation to produce sodium oxalate; Directly prepare the suspension sodium oxalate solution by solvent and be used for bottom production; Process and the aqueous sodium carbonate causticization of having removed aqueous sodium carbonate cooling washing sodium oxalate produce the residue contamination problem of environment, make sodium oxalate production reach environmental protection, energy-conservation, cleaner production.
(3) oxalic acid production utilization suspension sodium oxalate solution, add alcoholic solvent, add sulfuric acid reaction and obtain solid sulfur phase hydrochlorate, liquid phase oxalate diester, oxalic acid; Technology does not have to produce the metabisulfite solution be difficult to reclaim and the discharge of wastewater of rinsing influences environmental problem, makes oxalate diester, oxalic acid production reach environmental protection, energy-conservation, cleaner production.
(4) utilize the solid sodium sulfate after the rinsing to go drying and packaging to be finished product, technology becomes simply, economizes the evaporation of delead method oxalic acid rinsing liquid, spissated process, saves a large amount of steam, makes sodium sulfate salt production reach environmental protection, energy-conservation, cleaner production.
(5) reaction conditions is gentle, simple to operate in the entire reaction system, ratio between investments is low, and the derived product market capacity of product oxalate diester is big.
Description of drawings
The synoptic diagram of Fig. 1 reactive system of the present invention.
The infrared spectrogram of Fig. 2 solid sulfur phase hydrochlorate of the present invention.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
Among the present invention; Raw material be sodium formiate (production of sodium formiate utilizes the hot stove in ore deposit: the carbon monoxide of furnace of calcium carbide, tail gas of yellow phosphorus boiler through middle and high concentration under pressurized conditions with the alkaline reaction synthesising acid sodium; Be the carbon monoxide of China's invention fifties in last century, the method for caustic soda synthesising acid sodium in pipeline; Utilize the sodium formiate high-temperature dehydrogenation to change into sodium oxalate (referring to 2007 the 34th volume the 6th phases " experimental study of sodium formiate thermal decomposition behavior " of Beijing University of Chemical Technology's journal) then, but solubilizing agent wiring solution-forming disacidifyization.
Instance 1:
By the sodium oxalate solubilizing agent methyl alcohol wiring solution-forming after the sodium formiate dehydrogenation; In the stainless steel cauldron that has chuck, stirring, condensation reflux unit, add the sodium oxalate solution and the methyl alcohol 2～10Kg of returning that circulates that 15～20Kg prepares; Slowly drop into sulphur trioxide 7Kg, dme 4Kg reaction 6 hours; Stopped stirring sedimentation 2 hours, the taking-up of the upper strata stillness of night is decided to be solution 1#, takes out the middle level clear liquid again and returns sodium oxalate configuration solution.Add 2～15Kg methyl alcohol again and open stirring 1 hour, stopped stirring sedimentation 2 hours, supernatant liquid takes out and is decided to be solution 2#, and repeat above method and obtain solution 4-6#, cutting out partial oxalic acid (trace) and dimethyl oxalate, oxalic acid can be made product.Dimethyl oxalate develops downstream and adds water and get that oxalic acid, hydrogenation get terepthaloyl moietie, ammonification gets oxamide, and isolated methyl alcohol returns reaction, and solid phase is advanced the vacuum distilling drying plant, makes the powdered sodium sulfate product.
React to such an extent that dimethyl oxalate, methylcarbonate, methyl-formiate, oxalic acid (trace) amount to 9.5 kilograms, yield 95%.
Reaction soln: methanol solvate consumes 0.2 kilogram (the most of vaporization losses of participating in of alcohol).
Get 0.5 kilogram of above-mentioned dimethyl oxalate and add 1～4 kilogram pure water hydrolysis,, be heated to 90-120 ℃ and boiled 10～200 minutes with interior at the reaction kettle that has reflux, distillation tower, chuck heat exchange and whipping device.Vapor condensation reclaims separation of methanol to be distilled and water, and the water backwater is separated, methyl alcohol returns reaction cycle and uses.Liquid phase is separated oven dry through crystallisation by cooling and is obtained oxalic acid, confirms content through chemical examination, and Recycling Mother Solution is used (referring to Chinese invention patent " catalytic synthesis of oxalic acid from carbon monoxide, coupling process ").
Get 5 kilograms of hydrogenation hydrogenolysis of above-mentioned dimethyl oxalate, in having the tower of catalyst filling, in certain temperature, pressure, air speed scope; The product that obtains is through fractionation by distillation; Obtain methyl alcohol at 50～70 ℃, return reaction cycle and use, get 0.5 kilogram of ammonification ammonia of above-mentioned dimethyl oxalate and separate; Obtain solid suspension liquid through settlement separate oxamide and the ethanol of obtaining, ethanol returns the reaction cycle use, the oxamide product is quantitative through chromatographic qualitative.
Instance 2:
By the sodium oxalate solubilizing agent wiring solution-forming of sodium formiate after dehydrogenation; In the stainless steel cauldron that has chuck, stirring, condensation reflux unit, add the sodium oxalate solution and the methyl alcohol 200-1000Kg of returning that circulates that 1500Kg prepares; Slowly drop into methyl-sulfate 1100Kg reaction 8 hours, put into airtight vacuum rotary drum suction filtration machine, the solid phase wiring solution-forming advances next cover airtight vacuum rotary drum suction filtration machine; So carry out airtight vacuum rotary drum suction filtration machine suction filtration three times; Solid phase is advanced the vacuum distilling drying plant, and the high temperature vapor condensation gets liquid solution and returns reaction, oven dry back sodium sulfate salt.For the first time the suction filtration supernatant that gets solution go to cool off oxalic acid, dimethyl oxalate crystallization, supernatant liquid distillation back raffinate returns sodium oxalate preparation sodium oxalate solution, phlegma returns solid phase and makes solvent; The liquid phase that technology obtains is decided to be 2#, 3# solution, gets one ready and recycles, the solvent makeup that last solvent is returned by the rear portion distillation.
React to such an extent that oxalic acid, dimethyl oxalate, methylcarbonate, methyl-formiate amount to 980 kilograms (third-order reaction accumulative totals), yield 95%.
Reaction solvent: methanol solvate consumes 20 kilograms (the most of vaporization losseses of participating in of alcohol).
Instance 3
By the sodium oxalate solubilizing agent wiring solution-forming of sodium formiate after dehydrogenation; In the stainless steel cauldron that has chuck, stirring, condensation reflux unit, add the sodium oxalate solution and the methyl alcohol 200～1000Kg of returning that circulates that 1500Kg prepares; Slowly drop into sulphur trioxide 650Kg, dme 370Kg reaction 6 hours; Stopped stirring sedimentation 3 hours, the taking-up of the upper strata stillness of night is decided to be solution 1#, takes out the middle level stillness of night again and returns sodium oxalate configuration solution.Add 200～1500Kg methyl alcohol again and open stirring 0.5 hour, stopped stirring sedimentation 2 hours, the upper strata stillness of night takes out and is decided to be solution 2#; Add 200-1500Kg methyl alcohol again and open stirring 0.5 hour, put into airtight vacuum rotary drum suction filtration machine, solid phase is joined solution and is advanced next cover airtight vacuum rotary drum suction filtration machine; So carry out airtight vacuum rotary drum suction filtration machine suction filtration one to twice; Solid phase is advanced the vacuum distilling drying plant, and the high temperature vapor condensation gets liquid solution and returns reaction, oven dry back sodium sulfate salt.Reaction back for the first time the suction filtration supernatant that gets solution go to distill oxalic acid, dimethyl oxalate; Sodium oxalate preparation sodium oxalate solution returns in lower floor; Liquid phase is decided to be 3#-5# solution and gets ready and time recycle the solvent makeup that last solvent is returned by the rear portion distillation behind each airtight vacuum rotary drum suction filtration.
React to such an extent that oxalic acid, dimethyl oxalate, methylcarbonate, methyl-formiate amount to 980 kilograms (third-order reaction accumulative totals), yield 95%.
Reaction solvent: methanol solvate consumes 20 kilograms (the most of vaporization losseses of participating in of alcohol).
The foregoing description is after the preparation of accomplishing oxalic acid and oxalate diester, and Ke Jiashui is hydrolyzed, and perhaps hydrogenation carries out hydrogenolysis, and perhaps ammonification is carried out ammonia and separated.
Instance 4:
By the sodium oxalate solubilizing agent alcohol solution-forming after the sodium formiate dehydrogenation; In the stainless steel cauldron that has chuck, stirring, condensation reflux unit, add the sodium oxalate solution and the ethanol 2～10Kg of returning that circulates that 15～20Kg prepares; Slowly drop into sulphur trioxide 7Kg, diethyl ether 6Kg (ethanol) reaction 6 hours; Stopped stirring sedimentation 2 hours, the taking-up of the upper strata stillness of night is decided to be solution 1#, takes out the middle level clear liquid again and returns sodium oxalate configuration solution.Add 2～15Kg ethanol again and open stirring 1 hour, stopped stirring sedimentation 2 hours, supernatant liquid takes out and is decided to be solution 2#, and repeat above method and obtain solution 4-6#, cutting out partial oxalic acid (trace) and oxalic acid diethyl ester, oxalic acid can be made product.Oxalic acid diethyl ester develops downstream and adds water and get that oxalic acid, hydrogenation get terepthaloyl moietie, ammonification gets oxamide, and isolated methyl alcohol returns reaction, and solid phase is advanced the vacuum distilling drying plant, makes the powdered sodium sulfate product.
React to such an extent that oxalic acid diethyl ester, diethyl carbonate, ethyl formate, oxalic acid (trace) amount to 9.5 kilograms, yield 95%.
Reaction soln: alcohol solvent consumes 0.2 kilogram (the most of vaporization losses of participating in of alcohol).
Get 0.5 kilogram of above-mentioned oxalic acid diethyl ester and add 1～4 kilogram pure water hydrolysis,, be heated to 90-120 ℃ and boiled 10～200 minutes with interior at the reaction kettle that has reflux, distillation tower, chuck heat exchange and whipping device.Vapor condensation reclaims separating alcohol to be distilled and water, and the water backwater is separated, ethanol returns reaction cycle and uses.Liquid phase is separated oven dry through crystallisation by cooling and is obtained oxalic acid, confirms content through chemical examination, and Recycling Mother Solution is used (referring to Chinese invention patent " catalytic synthesis of oxalic acid from carbon monoxide, coupling process ").
Get 5 kilograms of hydrogenation hydrogenolysis of above-mentioned oxalic acid diethyl ester, in having the tower of catalyst filling, in certain temperature, pressure, air speed scope; The product that obtains is through fractionation by distillation; Obtain ethanol at 60～80 ℃, return reaction cycle and use, get 0.5 kilogram of ammonification ammonia of above-mentioned oxalic acid diethyl ester and separate; Obtain solid suspension liquid through settlement separate oxamide and the ethanol of obtaining, ethanol returns the reaction cycle use, the oxamide product is quantitative through chromatographic qualitative.
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. one kind is that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate, comprises first reaction member, second reaction member and the 3rd reaction member, it is characterized in that, wherein:
In said first reaction member, sodium formiate generates sodium oxalate through dehydrogenation reaction;
In said second reaction member, with sodium oxalate and solvent, to wherein adding sulfuric acid, carry out liquid-solid separation after the reaction then, wherein solid phase is a sodium sulfate salt, is rich in oxalate diester in the liquid phase;
In said the 3rd reaction member, the liquid phase that is rich in oxalate diester is carried out fractionation by distillation, then to oxalate diester be hydrolyzed respectively, hydrogenolysis and ammonia separates, and obtains alcohol, oxalic acid, terepthaloyl moietie and oxamide.
2. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate; It is characterized in that; In said first reaction member, raw material is a sodium formiate, and the production of sodium formiate utilizes the hot stove in ore deposit: the carbon monoxide of furnace of calcium carbide, tail gas of yellow phosphorus boiler through middle and high concentration pressurization, under the condition of heating with the alkaline reaction synthesising acid sodium; Utilize the sodium formiate high-temperature dehydrogenation to change into sodium oxalate, solubilizing agent wiring solution-forming desulfuration acid acidifying.
3. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate, it is characterized in that, in said second reaction member; Dehydrogenation adds solvent after processing sodium oxalate in system; To obtain suspension-s, then suspension-s is put into reactor drum, again to wherein adding sulfuric acid; React below being warming up to the boiling point of solvent simultaneously, question response finishes the back and adopts rinsing or suction filtration method to separate.
4. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate, it is characterized in that, in said second reaction member; Select alcohols as solvent, for example methyl alcohol, ethanol, propyl alcohol, butanols are to high carbon chain alcohol, after sodium oxalate is processed in the sodium formiate dehydrogenation; Add solvent dissolve and mix after obtain aaerosol solution; Then sodium oxalate suspension-s is put into reactor drum,, react below being warming up to the boiling point of selective solvent simultaneously to wherein adding sulfuric acid; The general at least 4 hours reaction times, can be preferred 4-12 hours.
5. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate; It is characterized in that; In said second reaction member; The sulfuric acid that adds selects directly to use oleum, methyl-sulfate or ethyl sulfate, also can add sulphur trioxide liquid and gas of dimethyl ether or diethyl ether gas, its elder generation is just contacted with sodium oxalate system at system's internal reaction moment generation methyl-sulfate or ethyl sulfate immediately react.
6. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate; It is characterized in that; In said second reaction member; Question response finishes the back and adopts rinsing or method of pumping filtration to carry out liquid-solid separation, wherein saidly separates as follows through rinsing: the reaction rear suspension liquid shifts out supernatant after sedimentation for a long time, and surplus throw out repeatedly washs with solvent; The washings of each washing stores to be got one ready and recycles, and last washings is provided by the solution that the distillation oxalate diester returns; Saidly separate as follows through filtering: the reaction rear suspension liquid is through the airtight vacuum suction filtration; Equipment is vacuum filtration groove, airtight vacuum suction filtration rotary drum, and for the first time solid phase is advanced the formulated suspension still behind the suction filtration, is mixed with suspension-s by a last circulation filtrating and carries out waiting for the second time, for the third time again and repeatedly filter; Liquid phase burring acid diesters distillation workshop section behind the suction filtration; Separate oxalate diester and solution, solution is pumpback filter formulated suspension again, and each circulation preparation suction filtration all leaches the oxalate diester in the solid materials.
7. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate; It is characterized in that; In said second reaction member, reaction generation solid sediment sodium sulfate salt and liquid phase oxalate diester, oxalate compound solution come out liquid phase separation through airtight siphon; Remove fractionation by distillation refined alcohol, oxalate diester, oxalic acid again; Solid phase through repeatedly rinsing, siphon separate POV sodium solid, the back in airtight negative pressure drying plant, steam slip, oven dry separates alcohol, alcohol is got back to reaction kettle and is recycled.
8. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate; It is characterized in that; In said the 3rd reaction member, the liquid phase that at first will be rich in oxalate diester carries out fractionation by distillation or low temperature crystallization separates, then the oxalate diester that obtains is developed respectively downstream be hydrolyzed, hydrogenolysis and ammonia separates; To obtain alcohol, oxalic acid, terepthaloyl moietie and oxamide, the alcohols material that wherein obtains can be circulated back in second reaction member and use.
9. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate; It is characterized in that; In said the 3rd reaction member, carry out fractionation by distillation to oxalic acid diethyl ester, the liquid product that is collected in 184 ℃-186 ℃ is an oxalic acid diethyl ester; Low temperature crystallization to dimethyl oxalate separates, and selects to carry out the crystallisation by cooling suction filtration below 50 degrees centigrade and gets the dimethyl oxalate crystal.
10. according to claim 1 a kind of be that raw material production is the chemical reaction system of main products with the oxalate diester with the sodium formiate; It is characterized in that; In the 3rd reaction member, said being hydrolyzed to utilizes oxalate diester under 80-110 ℃ of normal pressures, to boil with water; Said hydrogenolysis is oxalate diester hydrogenation synthesizing of ethylene glycol under the effect of catalyzer, and custom catalysts is copper chromium, copper chromium manganese, and temperature is 210-220 degree centigrade, and pressure is under the 2MPa, and one tunnel gas phase is a hydrogen, and one tunnel liquid phase is the oxalate diester charging, carries out hydrogenolysis; Said ammonia is separated to oxalate diester carries out ammonia with ammonia under normal pressure and is separated synthetic oxamide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162021A (en) * | 2017-07-04 | 2017-09-15 | 赤峰瑞阳化工有限公司 | A kind of sodium sulphate process for refining containing organic matter |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4663477A (en) * | 1986-03-27 | 1987-05-05 | Union Carbide Corporation | Process for the hydrolysis of dialkyl carbonates |
| CN1760179A (en) * | 2004-10-12 | 2006-04-19 | 山东新华万博化工有限公司 | Technique for preparing dimehtyl sulfate |
| CN101367718A (en) * | 2008-09-22 | 2009-02-18 | 贵州青利集团有限公司 | Method for preparing high-purity sodium formate with tail gas of yellow phosphorus stove |
| CN101462943A (en) * | 2009-01-08 | 2009-06-24 | 曹勇 | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate |
| CN101693656A (en) * | 2009-10-20 | 2010-04-14 | 山西省原平市化工有限责任公司 | High-conversion and high-yield process for producing oxalic acid by calcifying method |
| CN101869838A (en) * | 2009-04-24 | 2010-10-27 | 中国科学院福建物质结构研究所 | Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate |
| CN102249953A (en) * | 2011-05-20 | 2011-11-23 | 山东兴辉化工有限公司 | Method for converting dimethyl sulfate waste residue into dimethyl sulfate product |
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
| CN102351707A (en) * | 2011-11-18 | 2012-02-15 | 苏州诚和医药化学有限公司 | Method for preparing methyl o-anisate |
-
2012
- 2012-05-21 CN CN2012101593838A patent/CN102659584A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4663477A (en) * | 1986-03-27 | 1987-05-05 | Union Carbide Corporation | Process for the hydrolysis of dialkyl carbonates |
| CN1760179A (en) * | 2004-10-12 | 2006-04-19 | 山东新华万博化工有限公司 | Technique for preparing dimehtyl sulfate |
| CN101367718A (en) * | 2008-09-22 | 2009-02-18 | 贵州青利集团有限公司 | Method for preparing high-purity sodium formate with tail gas of yellow phosphorus stove |
| CN101462943A (en) * | 2009-01-08 | 2009-06-24 | 曹勇 | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate |
| CN101869838A (en) * | 2009-04-24 | 2010-10-27 | 中国科学院福建物质结构研究所 | Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate |
| CN101693656A (en) * | 2009-10-20 | 2010-04-14 | 山西省原平市化工有限责任公司 | High-conversion and high-yield process for producing oxalic acid by calcifying method |
| CN102249953A (en) * | 2011-05-20 | 2011-11-23 | 山东兴辉化工有限公司 | Method for converting dimethyl sulfate waste residue into dimethyl sulfate product |
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
| CN102351707A (en) * | 2011-11-18 | 2012-02-15 | 苏州诚和医药化学有限公司 | Method for preparing methyl o-anisate |
Non-Patent Citations (1)
| Title |
|---|
| 张天一: "合成草酸二乙酯的工艺优化", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》, 31 January 2005 (2005-01-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162021A (en) * | 2017-07-04 | 2017-09-15 | 赤峰瑞阳化工有限公司 | A kind of sodium sulphate process for refining containing organic matter |
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