CN102786410A - Treating method and apparatus for reaction solution produced in synthesis of glyoxalic acid through nitric acid oxidation of glyoxal - Google Patents
Treating method and apparatus for reaction solution produced in synthesis of glyoxalic acid through nitric acid oxidation of glyoxal Download PDFInfo
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Abstract
The invention provides a treating method and a treating apparatus for a reaction solution produced in synthesis of glyoxalic acid through nitric acid oxidation of glyoxal, belonging to the technical field of chemical industry. The treating method is as follows: a reaction solution which contains 10 to 25% of glyoxalic acid and is obtained in a main reaction during production of glyoxalic acid through nitric acid oxidation of glyoxal undergoes reduced pressure condensation in a primary condensation evaporator so as to remove a majority of lower-boiling acidic impurities, then undergoes crystallization and separation so as to remove the by-product oxalic acid and then undergoes secondary reduced pressure condensation so as to remove other impurities, and an obtained concentrate is diluted with purified water to prepare a glyoxalic acid product with a certain concentration, thereby achieving the purpose of separating and purifying glyoxalic acid. The apparatus comprises the primary condensation evaporator, a crystallization separator, a secondary condensation device and a concentrate diluting device. With such a treating method, yield of glyoxalic acid and product quality can be improved; and the production apparatus has the characteristics of low equipment investment, low energy consumption, a simple structure, convenient operation and the like and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of oxalic dialdehyde nitric acid oxidation and produce the reaction solution treatment process and the device thereof of oxoethanoic acid, belong to chemical technology field.
Background technology
Oxoethanoic acid is a kind of important Organic Chemicals, is widely used in the synthetic field of light industrial goods such as spices, medicine, agricultural chemicals, papermaking, coating, paint, leather and foodstuff additive.Process for production of glyoxalic acid can be divided into two big types of chemical synthesis and electrochemical synthesis methods, and the most frequently used in the industry have two kinds of oxalic dialdehyde nitric acid oxidation method and toxilic acid (acid anhydride) ozone oxidation methods.Wherein, the oxalic dialdehyde nitric acid oxidation method is with nitric acid as oxidant selective oxidation oxalic dialdehyde, and this method reaction conditions is gentle, and technology is simply ripe, and facility investment is few, is the main working method that at present domestic and international most of producer adopts.
In suitability for industrialized production with oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid; Oxidizing reaction gained reaction solution is a kind of mixed aqueous solution; Wherein contain purpose product oxoethanoic acid, by product oxalic acid, not oxidized oxalic dialdehyde, excessive nitric acid, hydrochloric acid and other impurity; How to take the post-treating method of high-level efficiency, less energy-consumption, high yield to isolate high-quality oxoethanoic acid product, this becomes the technical bottleneck that most of produces tartronic enterprise faces day by day.
Two patented claims of " a kind of oxoethanoic acid is made with extra care purifying plant 201120005225.8 " of mulberry field, Huanghua chemical industry ltd and " oxoethanoic acid process for refining and purifying and install 201110003631.5 " provide a kind of oxoethanoic acid process for purification and corollary apparatus.This method adopts the removal of impurity of two-stage simple distillation device, mainly utilizes second stage pyrogenic distillation to steam oxoethanoic acid.Though can effectively remove some impurity, through second stage pyrogenic distillation, oxoethanoic acid is at high temperature unstable, is prone to be destroyed; Cause yield very low, empirical tests, only this step yield is less than 70%; And energy consumption is higher, has increased substantially production cost, is not suitable for suitability for industrialized production.
The patent of invention of Wang Jinfeng " technological process of purifying and refining 200510105816.1 of oxoethanoic acid " realizes the isolating oxoethanoic acid process for purification of impurity though provide a kind of through anion-cation exchange resin and condensing crystal, and this method treatment effect is undesirable, and the anion-cation exchange resin processing power is extremely limited; And apparatus structure is complicated; Product yield is low, and facility investment is big, and production cost is higher; The resin regeneration complex steps, be inconvenient to operate; Especially refining back product chloride ion content is higher, has increased the product colour degree of depth, and its application is very limited.
The patent of invention of Tsing-Hua University " adopts the method 01131114.2 of the refining oxoethanoic acid of reaction, extraction " and adopts the mixed extractant multi-stage solvent extraction, then with the method purification oxoethanoic acid of the organic solvent condensing crystal of enriched products.This method is because of extraction with an organic solvent, and the extracting operation process is complicated, and product yield is low, and the raw material recovery is low, and production cost is high, is difficult to apply.
Through retrieval, up to the present, still do not have the more satisfactory oxoethanoic acid method for purification that is suitable for suitability for industrialized production and be disclosed.
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes prior art; A kind of oxidizing reaction liquid processing method that is very suitable for industrial mass production is provided, and it is low that this method has energy consumption, and yield is high; Characteristics such as cost is low, and products obtained therefrom is of light color, foreign matter content is low, use range is wide.
Another problem that will solve of the present invention provides the production equipment of realizing above-mentioned oxidizing reaction liquid processing method each item processing condition, and this device has production efficiency height, low equipment investment, characteristics such as simple in structure, easy to operate.
In order to solve above-mentioned two problems, the technical scheme that the present invention taked is:
The reaction solution treatment process that a kind of oxalic dialdehyde nitric acid oxidation is produced oxoethanoic acid may further comprise the steps:
(1) one-level concentrates: with oxoethanoic acid content is that the reaction solution of 10-25% drops into the one-level concentration evaporator and carries out concentrating under reduced pressure, and the vaporizer internal pressure is controlled at 5-95KPa, and feed temperature is controlled at 35-65 ℃ in the vaporizer, reaches 35-45% until oxoethanoic acid concentration.Collection distillates the acidic aqueous solution recycled, and liquid concentrator goes to crystallization kettle while hot.
(2) Crystallization Separation: liquid concentrator in the crystallization kettle was reduced to room temperature with water coolant in 1-2.5 hour; Continue in 1-2 hour, to be cooled to-2～3 ℃ insulation crystallization 0.5-1.5 hour, spinning then with icy salt solution; Remove the oxalic acid crystallization, filtrating changes the secondary concentration systems over to.
(3) secondary concentrates: change gained filtrating in the above-mentioned steps (2) over to the secondary concentration kettle and carry out concentrating under reduced pressure, the concentration kettle internal pressure is controlled at 5-95KPa, and feed temperature is controlled at 70-95 ℃ in the still, when feed liquid chloride ion content≤5ppm, finishes to concentrate.
(4) liquid concentrator dilution: under room temperature, gained liquid concentrator in the above-mentioned steps (3) is diluted to certain density aqueous glyoxylic acid finished product with purified water in blending jar.Wherein, the concentration of aqueous glyoxylic acid finished product is 40% or 50% in the step (4)
At one-level concentration evaporator described in the step (1) of described glyoxalic acid reaction liquid processing method is external heating type circulating evaporator (as shown in Figure 3), and the one-level concentration evaporator comprises equipment such as the outer well heater of shell and tube, separator, condensing surface, phlegma receiving tank, vacuum unit.
Acidic aqueous solution recycled to the oxidation main reaction system of in the step (1) of described glyoxalic acid reaction liquid processing method, collecting that distillates.
A kind of reaction solution treatment unit of oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid, whole set is combined by four relatively independent structural units such as one-level concentration evaporator, Crystallization Separation device, secondary concentrating unit, liquid concentrator air mix facilitieses.Wherein, The one-level concentration evaporator is the external heating type circulating evaporator; Characteristics such as this evaporation apparatus having heaters heat interchanging area is big, vaporization efficiency is high, concentration time is short, system does not have whisking appliance (rely under vaporised gas gas shock and the differing temps from convection current realizing the non-imposed stirring of material due to the liquid specific gravity difference), system vacuum degree height; Thereby efficiently solve the problem that oxoethanoic acid at high temperature is heated for a long time and causes product colour to be deepened, and can significantly improve production efficiency.
Described glyoxalic acid reaction liquid processing device, the one-level concentration evaporator comprises: heat interchanging area is the equipment such as vacuum unit that the outer well heater of the shell and tube of 50-100 ㎡, volume are the separator of 1500-3000L, condensing surface that heat interchanging area is 50-110 ㎡, volume is 1000-3000L phlegma receiving tank and vaporizer internal pressure can reach 5-95KPa; The Crystallization Separation device comprises: equipment such as crystallization kettle, whizzer; The secondary concentrating unit comprises: equipment such as concentration kettle, condensing surface, phlegma receiving tank, vacuum unit.The liquid concentrator air mix facilities comprises: blend equipment such as jar, material recycle pump, purified water test tank.
Described glyoxalic acid reaction liquid processing device; The pipe connection mode of each equipment of one-level concentration evaporator is as shown in Figure 2; The outlet of well heater links to each other with the import of separator; The outlet of separator links to each other with the import of condensing surface, and the outlet of condensing surface links to each other with the import that jar is received in reception, and the import that receives the outlet vacuum unit of receiving jar links to each other.
Described glyoxalic acid reaction liquid processing device; The equipment connection mode of one-level concentration evaporator main part is as shown in Figure 3; Tube still heater pipe upper edge separator tank body tangential direction links to each other with the separator middle and lower part, and separator end opening and tube still heater pipe bottom are with " 7 " font pipe connection, and the liquid stock opening for feed is distributed in tube still heater pipe bottom; Concentrate and accomplish liquid from the bottom outflow of separator awl bucket, the tube still heater heating medium is a steam.
The present invention is according to the physical property of various impurity in the reaction solution of synthesizing glyoxalic acid; Take effective ways to remove various impurity, solved energy consumption height in the prior art, yield is low; Cost is high, the problem that the products obtained therefrom color is dark, foreign matter content is high, use range is restricted.Device provided by the invention has production efficiency height, low equipment investment, characteristics such as simple in structure, easy to operate; Solve problems such as the existing apparatus production capacity is low, complex structure, facility investment is big, working cost is high, energy consumption is high, inconvenient operation, be applicable to the purification processes of oxidation liquid in the oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid technology.
Description of drawings
Fig. 1 is the process flow diagram of the reaction solution treatment process of oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid of the present invention.
Fig. 2 is an one-level thickening equipment schematic flow sheet of the present invention.
Fig. 3 is that one-level of the present invention concentrates external heating type circulating evaporator main part synoptic diagram.
Embodiment
Below in conjunction with accompanying drawing, the present invention is elaborated.
Like Fig. 1, Fig. 2, shown in Figure 3, implement to be equipped for:
Whole set is combined by four relatively independent structural units such as one-level concentration evaporator, Crystallization Separation device, secondary concentrating unit, liquid concentrator air mix facilitieses.The one-level concentration evaporator comprises: heat interchanging area is the equipment such as vacuum unit that the outer well heater of the shell and tube of 50-100 ㎡, volume are the separator of 1500-3000L, condensing surface that heat interchanging area is 50-110 ㎡, volume is 1000-3000L phlegma receiving tank and vaporizer internal pressure can reach 5-95KPa; The Crystallization Separation device comprises: equipment such as crystallization kettle, whizzer; The secondary concentrating unit comprises: equipment such as concentration kettle, condensing surface, phlegma receiving tank, vacuum unit.The liquid concentrator air mix facilities comprises: blend equipment such as jar, material recycle pump, purified water test tank.
The pipe connection mode of each equipment of one-level concentration evaporator is as shown in Figure 2; The outlet of well heater links to each other with the import of separator; The outlet of separator links to each other with the import of condensing surface, and the outlet of condensing surface links to each other with the import that jar is received in reception, and the import that receives the outlet vacuum unit of receiving jar links to each other.
The equipment connection mode of one-level concentration evaporator main part is as shown in Figure 3; Tube still heater pipe upper edge separator tank body tangential direction links to each other with the separator middle and lower part; Separator end opening and tube still heater pipe bottom are with " 7 " font pipe connection; The liquid stock opening for feed is distributed in tube still heater pipe bottom, concentrates completion liquid and flows out from separator awl bucket bottom, and the tube still heater heating medium is a steam.
As shown in Figure 1, implement according to following steps:
(1) one-level concentrates: with oxoethanoic acid content is that the reaction solution of 10-25% drops into the one-level concentration evaporator and carries out concentrating under reduced pressure, and the vaporizer internal pressure is controlled at 5-95KPa, and feed temperature is controlled at 35-65 ℃ in the vaporizer, reaches 35-45% until oxoethanoic acid concentration.Collection distillates the acidic aqueous solution recycled, and liquid concentrator goes to crystallization kettle while hot.
(2) Crystallization Separation: liquid concentrator in the crystallization kettle was reduced to room temperature with water coolant in 1-2.5 hour; Continue in 1-2 hour, to be cooled to-2～3 ℃ insulation crystallization 0.5-1.5 hour, spinning then with icy salt solution; Remove the oxalic acid crystallization, filtrating changes the secondary concentration systems over to.
(3) secondary concentrates: change gained filtrating in above-mentioned (2) over to the secondary concentration kettle and carry out concentrating under reduced pressure, the concentration kettle internal pressure is controlled at 5-95KPa, and feed temperature is controlled at 70-95 ℃ in the still, when feed liquid chloride ion content≤5ppm, finishes to concentrate.
(4) liquid concentrator dilution: under room temperature, gained liquid concentrator in above-mentioned (3) is diluted to the aqueous glyoxylic acid finished product of finite concentration (as: 40%, 50%) with purified water in blending jar.
After above-mentioned technological process finished, products obtained therefrom quality situation was (is example with 50% products): outward appearance is colourless to little yellow liquid, oxoethanoic acid content 50-50.5%, oxalic acid≤0.2%, oxalic dialdehyde≤0.1%, nitric acid≤0.01%, Cl
-≤5ppm, oxyacetic acid≤0.01%, salt≤0.01%.The yield situation is: the finished product oxoethanoic acid is to molar yield >=92% of oxoethanoic acid in the oxidation liquid.
In addition, those skilled in the art also can do other variation in spirit of the present invention, and certainly, these all should be included within the present invention's scope required for protection according to the variation that the present invention's spirit is done.
Embodiment 1
1, implement equipment:
Whole set is combined by four relatively independent structural units such as one-level concentration evaporator, Crystallization Separation device, secondary concentrating unit, liquid concentrator air mix facilitieses.The one-level concentration evaporator comprises: heat interchanging area is the equipment such as vacuum unit that the outer well heater of the shell and tube of 60 ㎡, volume are the separator of 1500L, condensing surface that heat interchanging area is 60 ㎡, volume is 1000L phlegma receiving tank and vaporizer internal pressure can reach 8KPa; The Crystallization Separation device comprises: 1000L crystallization kettle, SS-800 lining are moulded equipment such as whizzer; The secondary concentrating unit comprises: equipment such as 1000L concentration kettle, the graphite modified Vestolen PP 7052 condensing surface of 30 ㎡, 1000L phlegma receiving tank, vacuum unit.The liquid concentrator air mix facilities comprises: 2000L blends equipment such as jar, material recycle pump, purified water test tank.
The pipe connection mode of each equipment of one-level concentration evaporator is as shown in Figure 2; The outlet of well heater links to each other with the import of separator; The outlet of separator links to each other with the import of condensing surface, and the outlet of condensing surface links to each other with the import that jar is received in reception, and the import that receives the outlet vacuum unit of receiving jar links to each other.
The equipment connection mode of one-level concentration evaporator main part is as shown in Figure 3; Tube still heater pipe upper edge separator tank body tangential direction links to each other with the separator middle and lower part; Separator end opening and tube still heater pipe bottom are with " 7 " font pipe connection; The liquid stock opening for feed is distributed in tube still heater pipe bottom, concentrates completion liquid and flows out from separator awl bucket bottom, and the tube still heater heating medium is a steam.
2, implementation step:
(1) one-level concentrates: with oxoethanoic acid content is that 19% reaction solution drops into the one-level concentration evaporator and carries out concentrating under reduced pressure, and the vaporizer internal pressure is controlled at 8KPa, and feed temperature is controlled at 40-60 ℃ in the vaporizer, reaches 35% until oxoethanoic acid concentration.Collection distillates the acidic aqueous solution recycled, and liquid concentrator goes to crystallization kettle while hot.
(2) Crystallization Separation: liquid concentrator in the crystallization kettle was reduced to room temperature with water coolant in 2 hours, continue then in 1.5 hours, to be cooled to 1-3 ℃ with icy salt solution, insulation crystallization 1.5 hours, the oxalic acid crystallization is removed in spinning, and filtrating changes the secondary concentration systems over to.
(3) secondary concentrates: change gained filtrating in the above-mentioned steps (2) over to the secondary concentration kettle and carry out concentrating under reduced pressure, the concentration kettle internal pressure is controlled at 10KPa, and feed temperature is controlled at 75-90 ℃ in the still, when feed liquid chloride ion content≤5ppm, finishes to concentrate.
(4) liquid concentrator dilution: under room temperature, (the gained liquid concentrator is diluted to the aqueous glyoxylic acid finished product of oxoethanoic acid content 50% in the step 3) with purified water in blending jar with above-mentioned.
3, result of implementation:
After above-mentioned technological process finished, products obtained therefrom quality situation was: outward appearance is colourless to little yellow liquid, oxoethanoic acid content 50.1%, oxalic acid 0.18%, oxalic dialdehyde 0.08%, nitric acid 0.008%, Cl
-4.5ppm, oxyacetic acid 0.007%, salt 0.006%.The yield situation is: the finished product oxoethanoic acid is to the molar yield 93.1% of oxoethanoic acid in the oxidation liquid.
Embodiment 2
1, implement equipment:
Whole set by one-level concentrate, four relatively independent structural units such as Crystallization Separation, secondary concentrate, liquid concentrator dilution combine.The one-level concentration evaporator comprises: heat interchanging area is the equipment such as vacuum unit that the outer well heater of the shell and tube of 80 ㎡, volume are the separator of 2000L, condensing surface that heat interchanging area is 85 ㎡, volume is 1000L phlegma receiving tank and vaporizer internal pressure can reach 15KPa; The Crystallization Separation device comprises: 2000L crystallization kettle, SS-800 lining are moulded equipment such as whizzer; The secondary concentrating unit comprises: equipment such as 2000L concentration kettle, the graphite modified Vestolen PP 7052 condensing surface of 30 ㎡, 1000L phlegma receiving tank, vacuum unit.The liquid concentrator air mix facilities comprises: 2000L blends equipment such as jar, material recycle pump, purified water test tank.
The pipe connection mode of each equipment of one-level concentration evaporator is as shown in Figure 2; The outlet of well heater links to each other with the import of separator; The outlet of separator links to each other with the import of condensing surface, and the outlet of condensing surface links to each other with the import that jar is received in reception, and the import that receives the outlet vacuum unit of receiving jar links to each other.
The equipment connection mode of one-level concentration evaporator main part is as shown in Figure 3; Tube still heater pipe upper edge separator tank body tangential direction links to each other with the separator middle and lower part; Separator end opening and tube still heater pipe bottom are with " 7 " font pipe connection; The liquid stock opening for feed is distributed in tube still heater pipe bottom, concentrates completion liquid and flows out from separator awl bucket bottom, and the tube still heater heating medium is a steam.
2, implementation step:
(1) one-level concentrates: with oxoethanoic acid content is that 15.6% reaction solution drops into the one-level concentration evaporator and carries out concentrating under reduced pressure, and the vaporizer internal pressure is controlled at 15KPa, and feed temperature is controlled at 40-65 ℃ in the vaporizer, reaches 37.5% until oxoethanoic acid concentration.Collection distillates the acidic aqueous solution recycled, and liquid concentrator goes to crystallization kettle while hot.
(2) Crystallization Separation: liquid concentrator in the crystallization kettle was reduced to room temperature with water coolant in 1 hour, continue then in 1.5 hours, to be cooled to 1-1.5 ℃ with icy salt solution, insulation crystallization 0.5 hour, the oxalic acid crystallization is removed in spinning, and filtrating changes the secondary concentration systems over to.
(3) secondary concentrates: change gained filtrating in the above-mentioned steps (2) over to the secondary concentration kettle and carry out concentrating under reduced pressure, the concentration kettle internal pressure is controlled at 13KPa, and feed temperature is controlled at 60-90 ℃ in the still, when feed liquid chloride ion content≤5ppm, finishes to concentrate.
(4) liquid concentrator dilution: under room temperature, gained liquid concentrator in the above-mentioned steps (3) is diluted to the aqueous glyoxylic acid finished product of oxoethanoic acid content 50% with purified water in blending jar.
3, result of implementation:
After above-mentioned technological process finished, products obtained therefrom quality situation is: outward appearance was little yellow liquid, oxoethanoic acid content 50.3%, oxalic acid 0.19%, oxalic dialdehyde 0.1%, nitric acid 0.01%, Cl
-4ppm, oxyacetic acid 0.01%, salt 0.006%.The yield situation is: the finished product oxoethanoic acid is to the molar yield 94.5% of oxoethanoic acid in the oxidation liquid.
Embodiment 3
1, implement equipment:
Whole set by one-level concentrate, four relatively independent structural units such as Crystallization Separation, secondary concentrate, liquid concentrator dilution combine.The one-level concentration evaporator comprises: heat interchanging area is the equipment such as vacuum unit that the outer well heater of the shell and tube of 100 ㎡, volume are the separator of 3000L, condensing surface that heat interchanging area is 110 ㎡, volume is 2000L phlegma receiving tank and vaporizer internal pressure can reach 30KPa; The Crystallization Separation device comprises: 2000L crystallization kettle, SS-800 lining are moulded equipment such as whizzer; The secondary concentrating unit comprises: equipment such as 2000L concentration kettle, the graphite modified Vestolen PP 7052 condensing surface of 30 ㎡, 1000L phlegma receiving tank, vacuum unit.The liquid concentrator air mix facilities comprises: 3000L blends equipment such as jar, material recycle pump, purified water test tank.
The pipe connection mode of each equipment of one-level concentration evaporator is as shown in Figure 2; The outlet of well heater links to each other with the import of separator; The outlet of separator links to each other with the import of condensing surface, and the outlet of condensing surface links to each other with the import that jar is received in reception, and the import that receives the outlet vacuum unit of receiving jar links to each other.
The equipment connection mode of one-level concentration evaporator main part is as shown in Figure 3; Tube still heater pipe upper edge separator tank body tangential direction links to each other with the separator middle and lower part; Separator end opening and tube still heater pipe bottom are with " 7 " font pipe connection; The liquid stock opening for feed is distributed in tube still heater pipe bottom, concentrates completion liquid and flows out from separator awl bucket bottom, and the tube still heater heating medium is a steam.
2, implementation step:
(1) one-level concentrates: with oxoethanoic acid content is that 25% reaction solution drops into the one-level concentration evaporator and carries out concentrating under reduced pressure, and the vaporizer internal pressure is controlled at 30KPa, and feed temperature is controlled at 37-62 ℃ in the vaporizer, reaches 39.5% until oxoethanoic acid concentration.Collection distillates the acidic aqueous solution recycled, and liquid concentrator goes to crystallization kettle while hot.
(2) Crystallization Separation: liquid concentrator in the crystallization kettle was reduced to room temperature with water coolant in 2.5 hours, continue then in 2 hours, to be cooled to 1～2 ℃ with icy salt solution, insulation crystallization 0.5 hour, the oxalic acid crystallization is removed in spinning, and filtrating changes the secondary concentration systems over to.
(3) secondary concentrates: change gained filtrating in the above-mentioned steps (2) over to the secondary concentration kettle and carry out concentrating under reduced pressure, the concentration kettle internal pressure is controlled at 25KPa, and feed temperature is controlled at 70-93 ℃ in the still, when feed liquid chloride ion content≤5ppm, finishes to concentrate.
(4) liquid concentrator dilution: under room temperature, gained liquid concentrator in the above-mentioned steps (3) is diluted to the aqueous glyoxylic acid finished product of oxoethanoic acid content 50% with purified water in blending jar.
3, result of implementation:
After above-mentioned technological process finished, products obtained therefrom quality situation was: outward appearance is colourless to little yellow liquid, oxoethanoic acid content 50.45%, oxalic acid 0.2%, oxalic dialdehyde 0.1%, nitric acid 0.01%, Cl
-5ppm, oxyacetic acid 0.01%, salt 0.01%.The yield situation is: the finished product oxoethanoic acid is to the molar yield 95.7% of oxoethanoic acid in the oxidation liquid.
Claims (8)
1. the reaction solution treatment process of an oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid is characterized in that may further comprise the steps:
(1) one-level concentrates: with oxoethanoic acid content is that the reaction solution of 10-25% drops into the one-level concentration evaporator and carries out concentrating under reduced pressure, and the vaporizer internal pressure is controlled at
5-95KPa, feed temperature is controlled at 35-65 ℃ in the vaporizer, reaches 35-45% until oxoethanoic acid concentration,
Collection distillates the acidic aqueous solution recycled, and liquid concentrator goes to crystallization kettle while hot;
(2) Crystallization Separation: liquid concentrator in the crystallization kettle was reduced to room temperature with water coolant in 1-2.5 hour; Continue in 1-2 hour, to be cooled to-2～3 ℃ insulation crystallization 0.5-1.5 hour, spinning then with icy salt solution; Remove the oxalic acid crystallization, filtrating changes the secondary concentration systems over to;
(3) secondary concentrates: change gained filtrating in the above-mentioned steps (2) over to the secondary concentration kettle and carry out concentrating under reduced pressure, the concentration kettle internal pressure is controlled at 5-95KPa, and feed temperature is controlled at 70-95 ℃ in the still, when feed liquid chloride ion content≤5ppm, finishes to concentrate;
(4) liquid concentrator dilution: under room temperature, gained liquid concentrator in the above-mentioned steps (3) is diluted to certain density aqueous glyoxylic acid finished product with purified water in blending jar.
2. the reaction solution treatment process of oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid according to claim 1 is characterized in that, the concentration of aqueous glyoxylic acid finished product is 40% or 50% in the step (4).
3. the reaction solution treatment process of oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid according to claim 1 and 2; It is characterized in that; The one-level concentration evaporator is the external heating type circulating evaporator described in the step (1), and it comprises the outer well heater of shell and tube, separator, condensing surface, phlegma receiving tank, vacuum unit.
4. the reaction solution treatment process of oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid according to claim 1 and 2 is characterized in that, acidic aqueous solution recycled to the oxidation main reaction system of collecting described in the step (1) that distillates.
5. treatment unit that utilizes the reaction solution treatment process synthesizing glyoxalic acid reaction solution of each described oxalic dialdehyde nitric acid oxidation method synthesizing glyoxalic acid among the claim 1-4; It is characterized in that whole set is combined by one-level concentration evaporator, Crystallization Separation device, secondary concentrating unit, four relatively independent structural units of liquid concentrator air mix facilities.
6. the treatment unit of synthesizing glyoxalic acid reaction solution according to claim 5; It is characterized in that the one-level concentration evaporator comprises: heat interchanging area is the vacuum unit that the outer well heater of the shell and tube of 50-100 ㎡, volume are the separator of 1500-3000L, condensing surface that heat interchanging area is 50-110 ㎡, volume is 1000-3000L phlegma receiving tank and vaporizer internal pressure can reach 5-95KPa; The Crystallization Separation device comprises: crystallization kettle, whizzer; The secondary concentrating unit comprises: concentration kettle, condensing surface, phlegma receiving tank, vacuum unit; The liquid concentrator air mix facilities comprises: blend jar, material recycle pump, purified water test tank.
7. the treatment unit of synthesizing glyoxalic acid reaction solution according to claim 5; It is characterized in that; The pipe connection mode of each equipment of one-level concentration evaporator is: the outlet of well heater links to each other with the import of separator; The outlet of separator links to each other with the import of condensing surface, and the outlet of condensing surface links to each other with the import that jar is received in reception, and the import that receives the outlet vacuum unit of receiving jar links to each other.
8. the treatment unit of synthesizing glyoxalic acid reaction solution according to claim 5; It is characterized in that; The equipment connection mode of one-level concentration evaporator main part is: tube still heater pipe upper edge separator tank body tangential direction links to each other with the separator middle and lower part; Separator end opening and tube still heater pipe bottom are with " 7 " font pipe connection; The liquid stock opening for feed is distributed in tube still heater pipe bottom, concentrates completion liquid and flows out from separator awl bucket bottom, and the tube still heater heating medium is a steam.
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| CN109761800A (en) * | 2018-12-25 | 2019-05-17 | 兄弟科技股份有限公司 | The method of continuous crystallisation removing oxalic acid in glyoxalic acid production process |
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| CN109761800A (en) * | 2018-12-25 | 2019-05-17 | 兄弟科技股份有限公司 | The method of continuous crystallisation removing oxalic acid in glyoxalic acid production process |
| CN109761800B (en) * | 2018-12-25 | 2022-04-08 | 兄弟科技股份有限公司 | Method for removing oxalic acid by continuous crystallization in glyoxylic acid production process |
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