CN107986315A - The recovery method of mixed waste liquor - Google Patents
The recovery method of mixed waste liquor Download PDFInfo
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- CN107986315A CN107986315A CN201711250684.0A CN201711250684A CN107986315A CN 107986315 A CN107986315 A CN 107986315A CN 201711250684 A CN201711250684 A CN 201711250684A CN 107986315 A CN107986315 A CN 107986315A
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- mixed waste
- waste liquor
- recovery method
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/36—Nitrates
- C01F11/38—Preparation with nitric acid or nitrogen oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/36—Nitrates
- C01F11/44—Concentrating; Crystallisating; Dehydrating; Preventing the absorption of moisture or caking
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of recovery method of mixed waste liquor.A kind of recovery method of mixed waste liquor, contains acetic acid and nitric acid in mixed waste liquor, comprises the following steps：Calcium carbonate slurry progress neutralization reaction to no carbon dioxide is added into mixed waste liquor to overflow to obtain reaction solution；The pH value that the highly basic adjusting reaction solution is added into the reaction solution is 5~8；The reaction solution is carried out filtrate is obtained by filtration；Ca-Acetate crystals and mother liquor are obtained by filtration after carrying out heating evaporation crystallization treatment to the filtrate；Calcium nitrate crystal is obtained by filtration after carrying out crystallisation by cooling processing to the mother liquor.The recovery method technique of above-mentioned mixed waste liquor is simple, it is not necessary to is extracted or is distilled, energy consumption is low, and cost recovery is low, and acetic acid and nitric acid can be recycled at the same time.
Description
Technical field
The present invention relates to industrial wastes recovery technology field, more particularly to returning for the mixed waste liquor containing acetic acid and nitric acid
Receiving method.
Background technology
In liquid crystal display panel production process, useless etching of the substantial amounts of main component for phosphoric acid, acetic acid, nitric acid and water is produced
Liquid, for the resource recycling of the spent etching solution, can use and be concentrated by evaporation and crystallization processes production technical grade or electron level
Phosphoric acid, but the obtained acetic acid of evaporation and nitric acid mixing spent acid do not have good resource utilization method.The acetic acid of the mixing spent acid
Content is 10%~30%, and nitric acid content is 1%~8%, remaining is water.
There is researcher to use treatment by extraction acetic acid and nitric acid mixing spent acid, the extraction formed with tributyl phosphate and kerosene
It is extractant to take system, and by 5 grades of extractions, acetic acid extraction rate is up to 95.3%.Extraction phase first passes through highly basic processing and hot water wash
Wash, then distilled, realize the recycling of acetic acid and the regeneration of extractant, final acetic acid yield reaches 86.7%.Researcher
Also attempt to recycle acetic acid from acetic acid and nitric acid mixing spent acid with distillation combination method using part neutralization pretreatment, it is mixed by adding
1.02 times of sodium hydroxides of nitric acid equivalent, are fully neutralized with the nitric acid ensured in nitration mixture, are converted into sodium nitrate solution, so in acid
The process conditions such as the temperature of control distillation heating and distillation time afterwards, can be distilled to recover to obtain certain density acetic acid diluted, second
Acid recovering rate is up to 94.3%.
However, using above method when often results in acetic acid and nitric acid and can not separate, and by the way of extraction or distillation
Complex process, energy consumption are larger；Importantly, at present mixed waste liquor recovery method acetic acid can only be recycled and can not
Nitric acid is recycled.
The content of the invention
Based on this, it is necessary to for mixed waste liquor recovery process it is complicated, energy consumption is larger and nitric acid can not be recycled
The problem of, there is provided a kind of recovery method of mixed waste liquor.
A kind of recovery method of mixed waste liquor, contains acetic acid and nitric acid in the mixed waste liquor, comprises the following steps：
Calcium carbonate slurry progress neutralization reaction to no carbon dioxide is added into the mixed waste liquor to overflow to obtain instead
Answer liquid；
The pH value that the highly basic adjusting reaction solution is added into the reaction solution is 5~8；
The reaction solution is carried out filtrate is obtained by filtration；
Ca-Acetate crystals and mother liquor are obtained by filtration after carrying out heating evaporation crystallization treatment to the filtrate；
Calcium nitrate crystal is obtained by filtration after carrying out crystallisation by cooling processing to the mother liquor.
In a wherein embodiment, neutralization reaction is carried out to nothing in the calcium carbonate slurry that added into mixed waste liquor
The step of preparing the calcium carbonate slurry is further included before the step of carbon dioxide overflows to obtain reaction solution：
Under agitation, calcium carbonate is added to the water and disperses to form the calcium carbonate slurry；The calcium carbonate with it is described
The amount ratio of water is 0.2Kg/L~0.4Kg/L.
In a wherein embodiment, the amount ratio of the calcium carbonate slurry and the mixed waste liquor is 0.75:1~
1.25:1；
And/or the reaction temperature of the neutralization reaction is 40 DEG C~80 DEG C, reaction time of the neutralization reaction for 2h~
5h。
In a wherein embodiment, the highly basic in calcium hydroxide, potassium hydroxide and sodium hydroxide at least
It is a kind of.
In a wherein embodiment, the heating evaporation crystallization treatment is the absolute pressure in 80KPa~100KPa
Lower progress, the temperature of heating is 80 DEG C~100 DEG C.
In a wherein embodiment, heating evaporation crystallization treatment is carried out to the filtrate to the obtained mother liquor
Proportion is 1.31~1.36.
In a wherein embodiment, the heating evaporation crystallization treatment that carried out to the filtrate is to the obtained mother
The proportion of liquid be 1.31~1.36 the step of be specially：Continue heating evaporation knot after the mother liquor is merged with the filtrate
The proportion of crystalline substance processing to the mother liquor is 1.31~1.36.
In a wherein embodiment, acetic acid is obtained by filtration after the progress heating evaporation crystallization treatment to the filtrate
Step is further included after the step of calcium crystal and mother liquor：The Ca-Acetate crystals are rinsed using 70 DEG C~80 DEG C of water
To flushing liquor, and the flushing liquor is merged with the filtrate and carries out heating evaporation crystallization treatment.
In a wherein embodiment, the step of crystallisation by cooling processing, is specially：By the mother liquor slow cooling
To 10 DEG C~25 DEG C so that the calcium nitrate crystal separates out.
In a wherein embodiment, calcium nitrate crystalline substance is obtained by filtration after the progress crystallisation by cooling processing to the mother liquor
Step is further included after the step of body：The calcium nitrate crystal is rinsed using 20 DEG C~25 DEG C of water.
The recovery method of above-mentioned mixed waste liquor, using the acetic acid and nitric acid reaction in calcium carbonate slurry and waste liquid, and is adjusted
The pH value of reaction solution for 5~8 so that the filtrate containing calcium acetate and calcium nitrate is obtained by filtration after fully reacting in acetic acid and nitric acid, and
Heating evaporation crystallization treatment is first carried out to obtain Ca-Acetate crystals, then carries out crystallisation by cooling and handles to obtain calcium nitrate crystal, so that
So that the acetic acid and nitric acid in waste water are recovered in the form of Ca-Acetate crystals and calcium nitrate crystal respectively, above-mentioned mixed waste liquor
Recovery method technique is simple, it is not necessary to is extracted or is distilled, energy consumption is low, and cost recovery is low, and can be at the same time to acetic acid and nitre
Acid is recycled.
Brief description of the drawings
Fig. 1 is the process flow chart of the recovery method of the mixed waste liquor of an embodiment.
Embodiment
The recovery method of mixed waste liquor is described in further detail below in conjunction with embodiment and attached drawing.
Referring to Fig. 1, the recovery method of the mixed waste liquor of an embodiment, contain acetic acid and nitric acid in mixed waste liquor, wrap
Include following steps：
S110, prepare calcium carbonate slurry.
In a wherein embodiment, under agitation, calcium carbonate is added to the water and disperses to form calcium carbonate slurry.
Further, calcium carbonate slurry is suspension.
In a wherein embodiment, the amount ratio of calcium carbonate and water is 0.2Kg/L~0.4Kg/L.
S120, into mixed waste liquor, addition calcium carbonate slurry progress neutralization reaction to no carbon dioxide overflows to obtain instead
Answer liquid.
In a wherein embodiment, operation is stirred when calcium carbonate slurry is added into mixed waste liquor.Further
, it is 50rpm~300rpm that mixing speed is controlled when being stirred operation.
In a wherein embodiment, made when calcium carbonate slurry is added into mixed waste liquor by the way of being progressively added dropwise
Spilling that is uniform and preventing slurry and waste liquid must be reacted, the charging rate of calcium carbonate slurry is 1Kg/min~20Kg/min.
In a wherein embodiment, temperature when carrying out neutralization reaction is 40 DEG C~80 DEG C, carries out neutralization reaction
Time is 2h~5h.
In a wherein embodiment, the amount ratio of calcium carbonate slurry and mixed waste liquor is 0.75:1~1.25:1.
S130, the pH value that addition highly basic adjusts reaction solution into reaction solution are 5~8.
In a wherein embodiment, highly basic is selected from least one of calcium hydroxide, potassium hydroxide and sodium hydroxide.
Preferably, highly basic is calcium hydroxide, other cations are introduced to avoid in reaction solution.
Further, highly basic is added in reaction solution in the form of strong alkali aqueous solution, and the mass concentration of strong alkali aqueous solution is
0.01%~20%.
Acetic acid and nitric acid in waste liquid can be enabled for 5~8 by highly basic is added into reaction solution adjusting the pH value of reaction solution
Enough fully reactions.
S140, carry out reaction solution filtrate is obtained by filtration.
In a wherein embodiment, reaction solution is filtered to remove the insoluble matter in reaction solution.Further,
To first carry out that filtrate is obtained by filtration again after reaction solution stewing process 0.5h~1h.
S150, be obtained by filtration Ca-Acetate crystals and mother liquor after carrying out heating evaporation crystallization treatment to filtrate.
In a wherein embodiment, heating evaporation crystallization treatment be under the absolute pressure of 80KPa~100KPa into
OK, the temperature of heating is 80 DEG C~100 DEG C.
In a wherein embodiment, the proportion that heating evaporation crystallization treatment to obtained mother liquor are carried out to filtrate is
1.31~1.36.When the concentration of calcium nitrate in mother liquor is relatively low, the proportion of mother liquor is between 1.19~1.31；And with mother liquor
The concentration increase of calcium nitrate, the concentration of mother liquor increase to 1.31~1.36, and at this time, calcium nitrate is progressivelyed reach or approached and is full in mother liquor
With.
In a wherein embodiment, the proportion that heating evaporation crystallization treatment to obtained mother liquor are carried out to filtrate is
1.31~1.36 the step of is specially：Continue heating evaporation crystallization treatment after mother liquor is merged with filtrate to the proportion of mother liquor
For 1.31~1.36.
S160, using 70 DEG C~80 DEG C of water be rinsed Ca-Acetate crystals.
Recycle and rinse in a wherein embodiment, after being rinsed using 70 DEG C~80 DEG C of water to Ca-Acetate crystals
Liquid, then flushing liquor is merged with filtrate and continues heating evaporation crystallization treatment.
S170, be dried Ca-Acetate crystals processing.
In a wherein embodiment, Ca-Acetate crystals are placed at 60 DEG C~70 DEG C and carry out vacuum drying treatment, into
The time of row vacuum drying treatment is 0.5h~10h.
S180, be obtained by filtration calcium nitrate crystal after mother liquor is carried out crystallisation by cooling processing.
In a wherein embodiment, crystallisation by cooling processing the step of be specially：By mother liquor slow cooling to 10 DEG C~
25 DEG C so that calcium nitrate crystal separates out.
In a wherein embodiment, the time for carrying out crystallisation by cooling processing is 1h~20h.
In a wherein embodiment, mother liquor is subjected to filtering so as to obtain calcium nitrate crystalline substance after the precipitation of calcium nitrate crystal
Body and supernatant.
In a wherein embodiment, continue after obtained supernatant is merged with the filtrate obtained in step S140 into
Row heating evaporation crystallization treatment, to improve the rate of recovery of acetic acid and nitric acid in waste liquid.
S190, using 20 DEG C~25 DEG C of water be rinsed calcium nitrate crystal.
Recycle and rinse in a wherein embodiment, after being rinsed using 20 DEG C~25 DEG C of water to calcium nitrate crystal
Liquid, then flushing liquor is merged with filtrate and continues heating evaporation crystallization treatment.
In a wherein embodiment, by calcium nitrate after being rinsed using 20 DEG C~25 DEG C of water to calcium nitrate crystal
Crystal is placed in progress vacuum drying treatment at 30 DEG C~35 DEG C and obtains four water-calcium nitrate product.
In a wherein embodiment, the time for carrying out vacuum drying treatment is 0.5h~10h.
The recovery method of above-mentioned mixed waste liquor, using the acetic acid and nitric acid reaction in calcium carbonate slurry and waste liquid, and is adjusted
The pH value of reaction solution for 5~8 so that the filtrate containing calcium acetate and calcium nitrate is obtained by filtration after fully reacting in acetic acid and nitric acid, and
Heating evaporation crystallization treatment is first carried out to obtain Ca-Acetate crystals, then carries out crystallisation by cooling and handles to obtain calcium nitrate crystal, so that
So that the acetic acid and nitric acid in waste water are recovered in the form of Ca-Acetate crystals and calcium nitrate crystal respectively, above-mentioned mixed waste liquor
Recovery method technique is simple, it is not necessary to is extracted or is distilled, energy consumption is low, and cost recovery is low, and can be at the same time to acetic acid and nitre
Acid is recycled.
It should be noted that in other embodiments, step S110, step S160, step S170 and step S190 are equal
It can be omitted.
Here is the explanation of specific embodiment.
Embodiment 1
(1) under the speed of agitator of 80rpm, the calcium carbonate of 248Kg is added in the water of 800L and disperses to form calcium carbonate
Slurry.
(2) under the speed of agitator of 100rpm, it is gradually added into the mixed waste liquor of 1000L obtained in step (1)
Calcium carbonate slurry carries out neutralization reaction to no carbon dioxide and overflows to obtain reaction solution.Wherein, acetic acid contains in mixed waste liquor
Measure as 23%, the content of nitric acid is 5%；The temperature for carrying out neutralization reaction is 80 DEG C, and the time for carrying out neutralization reaction is 2h.
(3) mass concentration that 5Kg is added into reaction solution is that 10% calcium hydroxide aqueous solution adjusts the pH value of reaction solution
For 8.
(4) after reaction solution being stood 0.5h carry out that filtrate is obtained by filtration.
(5) under the absolute pressure of 100KPa, filtrate is heated to 80 DEG C of progress heating evaporation crystallization treatment to proportions is
After 1.19, Ca-Acetate crystals and mother liquor are obtained by filtration while hot；Mother liquor is merged with filtrate and continues heating evaporation crystallization treatment,
And 23 proportions to mother liquor are repeated as 1.36 so that the calcium nitrate in mother liquor reaches or close to saturation.
(6) obtained Ca-Acetate crystals are rinsed using 80 DEG C of the hot water of 20Kg, the flushing liquor that recycling is obtained
Mixed with the filtrate obtained in step (4) and continue heating evaporation crystallization treatment, obtained Ca-Acetate crystals are placed in 60 DEG C
Lower progress vacuum drying treatment 3h obtains a water acetic acid calcium product.
(7) the mother liquor slow cooling that proportion is 1.36 is carried out crystallisation by cooling to 10 DEG C to handle so that the analysis of calcium nitrate crystal
Go out, calcium nitrate crystal and supernatant is obtained by filtration；Supernatant is merged with the filtrate obtained in step (4) and continues heating steaming
Send out crystallization treatment.
(8) obtained calcium nitrate crystal is rinsed using 20 DEG C of the water of 20Kg, will recycle obtained flushing liquor with
The filtrate mixing obtained in step (4) continues heating evaporation crystallization treatment, and obtained calcium nitrate crystal is placed at 30 DEG C
Carry out vacuum drying treatment and obtain four water-calcium nitrate product.
In the present embodiment, the rate of recovery of acetic acid is 95.6%, and the rate of recovery of nitric acid is 76.8%.In order to improve acetic acid and
The rate of recovery of nitric acid, all filtrates and flushing liquor can be with circulation and stress, and the rate of recovery of final acetic acid and the rate of recovery of nitric acid can
Reach more than 99%.
Embodiment 2
(1) under the speed of agitator of 80rpm, the calcium carbonate of 310Kg is added in the water of 950L and disperses to form calcium carbonate
Slurry.
(2) under the speed of agitator of 100rpm, it is gradually added into the mixed waste liquor of 1250L obtained in step (1)
Calcium carbonate slurry carries out neutralization reaction to no carbon dioxide and overflows to obtain reaction solution.Wherein, acetic acid contains in mixed waste liquor
Measure as 30%, the content of nitric acid is 8%；The temperature for carrying out neutralization reaction is 50 DEG C, and the time for carrying out neutralization reaction is 5h.
(3) mass concentration that 20Kg is added into reaction solution is that 1.5% calcium hydroxide aqueous solution adjusts the pH of reaction solution
It is worth for 6.
(4) after reaction solution being stood 1h carry out that filtrate is obtained by filtration.
(5) under the absolute pressure of 90KPa, filtrate is heated to 100 DEG C of progress heating evaporation crystallization treatment to proportions is
After 1.21, Ca-Acetate crystals and mother liquor are obtained by filtration while hot；Mother liquor is merged with filtrate and continues heating evaporation crystallization treatment,
And 26 proportions to mother liquor are repeated as 1.31 so that the calcium nitrate in mother liquor reaches or close to saturation.
(6) obtained Ca-Acetate crystals are rinsed using 70 DEG C of the hot water of 30Kg, the flushing liquor that recycling is obtained
Mixed with the filtrate obtained in step (4) and continue heating evaporation crystallization treatment, obtained Ca-Acetate crystals are placed in 65 DEG C
Lower progress vacuum drying treatment 10h obtains a water acetic acid calcium product.
(7) the mother liquor slow cooling that proportion is 1.31 is carried out crystallisation by cooling to 25 DEG C to handle so that the analysis of calcium nitrate crystal
Go out, calcium nitrate crystal and supernatant is obtained by filtration；Supernatant is merged with the filtrate obtained in step (4) and continues heating steaming
Send out crystallization treatment.
(8) obtained calcium nitrate crystal is rinsed using 25 DEG C of the water of 30Kg, will recycle obtained flushing liquor with
The filtrate mixing obtained in step (4) continues heating evaporation crystallization treatment, and obtained calcium nitrate crystal is placed at 30 DEG C
Carry out vacuum drying treatment and obtain four water-calcium nitrate product.
In the present embodiment, the rate of recovery of acetic acid is 89.9%, and the rate of recovery of nitric acid is 81.5%.In order to improve acetic acid and
The rate of recovery of nitric acid, all filtrates and flushing liquor can be with circulation and stress, and the rate of recovery of final acetic acid and the rate of recovery of nitric acid can
Reach more than 99%.
Embodiment 3
(1) under the speed of agitator of 50rpm, the calcium carbonate of 150Kg is added in the water of 600L and disperses to form calcium carbonate
Slurry.
(2) under the speed of agitator of 50rpm, obtained carbon in step (1) is gradually added into the mixed waste liquor of 1000L
Sour calcium slurry carries out neutralization reaction to no carbon dioxide and overflows to obtain reaction solution.Wherein, in mixed waste liquor acetic acid content
For 10%, the content of nitric acid is 8%；The temperature for carrying out neutralization reaction is 40 DEG C, and the time for carrying out neutralization reaction is 2h.
(3) mass concentration that 3Kg is added into reaction solution is that 20% calcium hydroxide aqueous solution adjusts the pH value of reaction solution
For 8.
(4) after reaction solution being stood 0.5h carry out that filtrate is obtained by filtration.
(5) under the absolute pressure of 100KPa, filtrate is heated to 80 DEG C of progress heating evaporation crystallization treatment to proportions is
After 1.19, Ca-Acetate crystals and mother liquor are obtained by filtration while hot；Mother liquor is merged with filtrate and continues heating evaporation crystallization treatment,
And the proportion being repeated 12 times to mother liquor for 1.36 so that the calcium nitrate in mother liquor reaches or close to saturation.
(6) obtained Ca-Acetate crystals are rinsed using 80 DEG C of the hot water of 20Kg, the flushing liquor that recycling is obtained
Mixed with the filtrate obtained in step (4) and continue heating evaporation crystallization treatment, obtained Ca-Acetate crystals are placed in 60 DEG C
Lower progress vacuum drying treatment 1h obtains a water acetic acid calcium product.
(7) the mother liquor slow cooling that proportion is 1.36 is carried out crystallisation by cooling to 10 DEG C to handle so that the analysis of calcium nitrate crystal
Go out, calcium nitrate crystal and supernatant is obtained by filtration；Supernatant is merged with the filtrate obtained in step (4) and continues heating steaming
Send out crystallization treatment.
(8) obtained calcium nitrate crystal is rinsed using 20 DEG C of the water of 20Kg, will recycle obtained flushing liquor with
The filtrate mixing obtained in step (4) continues heating evaporation crystallization treatment, and obtained calcium nitrate crystal is placed at 30 DEG C
Carry out vacuum drying treatment and obtain four water-calcium nitrate product.
In the present embodiment, the rate of recovery of acetic acid is 88.2%, and the rate of recovery of nitric acid is 78.3%.In order to improve acetic acid and
The rate of recovery of nitric acid, all filtrates and flushing liquor can be with circulation and stress, and the rate of recovery of final acetic acid and the rate of recovery of nitric acid can
Reach more than 99%.
Embodiment 4
(1) under the speed of agitator of 150rpm, the calcium carbonate of 280Kg is added in the water of 1200L and disperses to form carbonic acid
Calcium slurry.
(2) under the speed of agitator of 300rpm, it is gradually added into the mixed waste liquor of 1000L obtained in step (1)
Calcium carbonate slurry carries out neutralization reaction to no carbon dioxide and overflows to obtain reaction solution.Wherein, acetic acid contains in mixed waste liquor
Measure as 30%, the content of nitric acid is 1%；The temperature for carrying out neutralization reaction is 80 DEG C, and the time for carrying out neutralization reaction is 4h.
(3) mass concentration that 30Kg is added into reaction solution is that 11% calcium hydroxide aqueous solution adjusts the pH value of reaction solution
For 8.
(4) after reaction solution being stood 0.5h carry out that filtrate is obtained by filtration.
(5) under the absolute pressure of 100KPa, filtrate is heated to 80 DEG C of progress heating evaporation crystallization treatment to proportions is
After 1.19, Ca-Acetate crystals and mother liquor are obtained by filtration while hot；Mother liquor is merged with filtrate and continues heating evaporation crystallization treatment,
And 33 proportions to mother liquor are repeated as 1.36 so that the calcium nitrate in mother liquor reaches or close to saturation.
(6) obtained Ca-Acetate crystals are rinsed using 80 DEG C of the hot water of 20Kg, the flushing liquor that recycling is obtained
Mixed with the filtrate obtained in step (4) and continue heating evaporation crystallization treatment, obtained Ca-Acetate crystals are placed in 60 DEG C
Lower progress vacuum drying treatment 3h obtains a water acetic acid calcium product.
(7) the mother liquor slow cooling that proportion is 1.36 is carried out crystallisation by cooling to 10 DEG C to handle so that the analysis of calcium nitrate crystal
Go out, calcium nitrate crystal and supernatant is obtained by filtration；Supernatant is merged with the filtrate obtained in step (4) and continues heating steaming
Send out crystallization treatment.
(8) obtained calcium nitrate crystal is rinsed using 20 DEG C of the water of 20Kg, will recycle obtained flushing liquor with
The filtrate mixing obtained in step (4) continues heating evaporation crystallization treatment, and obtained calcium nitrate crystal is placed at 30 DEG C
Carry out vacuum drying treatment and obtain four water-calcium nitrate product.
In the present embodiment, the rate of recovery of acetic acid is 96.1%, and the rate of recovery of nitric acid is 86.9%.In order to improve acetic acid and
The rate of recovery of nitric acid, all filtrates and flushing liquor can be with circulation and stress, and the rate of recovery of final acetic acid and the rate of recovery of nitric acid can
Reach more than 99%.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously
Cannot therefore it be construed as limiting the scope of the patent.It should be pointed out that come for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of recovery method of mixed waste liquor, contain acetic acid and nitric acid in the mixed waste liquor, it is characterised in that including following
Step：
Calcium carbonate slurry progress neutralization reaction to no carbon dioxide is added into the mixed waste liquor to overflow to obtain reaction solution；
The pH value that the highly basic adjusting reaction solution is added into the reaction solution is 5~8；
The reaction solution is carried out filtrate is obtained by filtration；
Ca-Acetate crystals and mother liquor are obtained by filtration after carrying out heating evaporation crystallization treatment to the filtrate；
Calcium nitrate crystal is obtained by filtration after carrying out crystallisation by cooling processing to the mother liquor.
2. the recovery method of mixed waste liquor according to claim 1, it is characterised in that added described into mixed waste liquor
Further included before the step of calcium carbonate slurry progress neutralization reaction to no carbon dioxide overflows to obtain reaction solution and prepare the carbon
The step of sour calcium slurry：
Under agitation, calcium carbonate is added to the water and disperses to form the calcium carbonate slurry；The calcium carbonate and the water
Amount ratio is 0.2Kg/L~0.0.4Kg/L.
3. the recovery method of mixed waste liquor according to claim 2, it is characterised in that the calcium carbonate slurry is mixed with described
The mass ratio for closing waste liquid is 0.75:1~1.25:1；
And/or the reaction temperature of the neutralization reaction is 40 DEG C~80 DEG C, the reaction time of the neutralization reaction is 2h~5h.
4. the recovery method of mixed waste liquor according to claim 1, it is characterised in that the highly basic be selected from calcium hydroxide,
At least one of potassium hydroxide and sodium hydroxide.
5. the recovery method of mixed waste liquor according to claim 1, it is characterised in that the heating evaporation crystallization treatment is
Carried out under the absolute pressure of 80KPa~100KPa, the temperature of heating is 80 DEG C~100 DEG C.
6. the recovery method of mixed waste liquor according to claim 1, it is characterised in that heating evaporation is carried out to the filtrate
The proportion of crystallization treatment to the obtained mother liquor is 1.31~1.36.
7. the recovery method of mixed waste liquor according to claim 6, it is characterised in that described to be heated to the filtrate
Evaporative crystallization handle to the obtained mother liquor proportion be 1.31~1.36 the step of be specially：By the mother liquor and the filter
Liquid continues heating evaporation crystallization treatment to mother liquor proportion after merging is 1.31~1.36.
8. the recovery method of mixed waste liquor according to claim 1, it is characterised in that described to be heated to the filtrate
Step is further included after the step of Ca-Acetate crystals and mother liquor is obtained by filtration after evaporative crystallization processing：Using 70 DEG C~80 DEG C of water
The Ca-Acetate crystals are rinsed to obtain flushing liquor, and the flushing liquor is merged with the filtrate and carries out heating evaporation knot
Crystalline substance processing.
9. the recovery method of mixed waste liquor according to claim 1, it is characterised in that the step of crystallisation by cooling is handled
Specially：By the mother liquor slow cooling to 10 DEG C~25 DEG C so that the calcium nitrate crystal separates out.
10. the recovery method of mixed waste liquor according to claim 1, it is characterised in that described cold to mother liquor progress
But step is further included after the step of calcium nitrate crystal is obtained by filtration after crystallization treatment：Using 20 DEG C~25 DEG C of water to the nitre
Sour calcium crystal is rinsed.
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