CN107986315B - The recovery method of mixed waste liquor - Google Patents
The recovery method of mixed waste liquor Download PDFInfo
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- CN107986315B CN107986315B CN201711250684.0A CN201711250684A CN107986315B CN 107986315 B CN107986315 B CN 107986315B CN 201711250684 A CN201711250684 A CN 201711250684A CN 107986315 B CN107986315 B CN 107986315B
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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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Abstract
The present invention relates to a kind of recovery methods of mixed waste liquor.A kind of recovery method of mixed waste liquor contains acetic acid and nitric acid in mixed waste liquor, comprising the following steps: calcium carbonate slurry is added into mixed waste liquor carries out neutralization reaction to no carbon dioxide gas and overflow to obtain reaction solution；It is 5~8 that highly basic is added into the reaction solution and adjusts the pH value of the reaction solution；It is filtered the reaction solution to obtain filtrate；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 simple process of above-mentioned mixed waste liquor, does not need to be extracted or be distilled, and low energy consumption, and cost recovery is low, and can be recycled simultaneously to acetic acid and nitric acid.
Description
Technical field
The present invention relates to industrial wastes recovery technology fields, more particularly to returning for the mixed waste liquor containing acetic acid and nitric acid
Receiving method.
Background technique
In liquid crystal display panel production process, the useless etching that a large amount of main component is phosphoric acid, acetic acid, nitric acid and water is generated
Liquid can produce technical grade or electron level with crystallization processes using being concentrated by evaporation for the resource recycling of the spent etching solution
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 using treatment by extraction acetic acid and nitric acid mixing spent acid, the extraction formed with tributyl phosphate and kerosene
Taking system is extractant, is extracted by 5 grades, acetic acid extraction rate is up to 95.3%.Extraction phase first passes through highly basic processing and hot water wash
It washs, then is distilled, realize the recycling of acetic acid and the regeneration of extractant, final acetic acid yield reaches 86.7%.Researcher
It also attempts 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 being added
1.02 times of sodium hydroxides of nitric acid equivalent, are fully neutralized with the nitric acid guaranteed 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, often resulting in acetic acid and nitric acid when using the above method 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.
Summary of the invention
Based on this, it is necessary to for mixed waste liquor recovery process it is complicated, energy consumption is larger and can not recycle to nitric acid
The problem of, a kind of recovery method of mixed waste liquor is provided.
A kind of recovery method of mixed waste liquor contains acetic acid and nitric acid in the mixed waste liquor, comprising the following steps:
Calcium carbonate slurry progress neutralization reaction to no carbon dioxide gas is added into the mixed waste liquor to overflow to obtain instead
Answer liquid；
It is 5~8 that highly basic is added into the reaction solution and adjusts the pH value of the reaction solution；
It is filtered the reaction solution to obtain filtrate；
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 is added into mixed waste liquor
Carbon dioxide gas further includes the steps that preparing the calcium carbonate slurry before overflowing the step of obtaining reaction solution:
Under agitation, calcium carbonate is added to the water dispersion and forms 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 be 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 be 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 are 80 DEG C~100 DEG C.
In a wherein embodiment, heating evaporation crystallization treatment is carried out to the obtained mother liquor to the filtrate
Specific gravity is 1.31~1.36.
It is described that heating evaporation crystallization treatment is carried out to the obtained mother to the filtrate in a wherein embodiment
The step of specific gravity of liquid is 1.31~1.36 specifically: continue heating evaporation knot after merging the mother liquor with the filtrate
The specific gravity 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
It further comprises the steps of: after the step of calcium crystal and mother liquor and the Ca-Acetate crystals is 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 crystallisation by cooling processing the step of specifically: by the mother liquor slow cooling
To 10 DEG C~25 DEG C the calcium nitrate crystal is precipitated.
In a wherein embodiment, calcium nitrate crystalline substance is obtained by filtration after the progress crystallisation by cooling processing to the mother liquor
It further comprises the steps of: after the step of body and 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 filtrate containing calcium acetate and calcium nitrate is obtained by filtration after for 5~8 acetic acid and nitric acid sufficiently being reacted in the pH value of reaction solution, and
It carries out heating evaporation crystallization treatment first to obtain Ca-Acetate crystals, then carries out crystallisation by cooling and handle to obtain calcium nitrate crystal, thus
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 simple process is not needed to be extracted or be distilled, and low energy consumption, and cost recovery is low, and can be simultaneously to acetic acid and nitre
Acid is recycled.
Detailed description of the invention
Fig. 1 is the process flow chart of the recovery method of the mixed waste liquor of an embodiment.
Specific embodiment
The recovery method of mixed waste liquor is described in further detail below in conjunction with specific embodiment and attached drawing.
Referring to Fig. 1, the recovery method of the mixed waste liquor of an embodiment, acetic acid and nitric acid, packet are contained in mixed waste liquor
Include following steps:
S110, calcium carbonate slurry is prepared.
In a wherein embodiment, under agitation, calcium carbonate is added to the water dispersion and forms 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 gas overflows to obtain instead
Answer liquid.
In a wherein embodiment, operation is stirred when calcium carbonate slurry being added into mixed waste liquor.Further
, control mixing speed is 50rpm~300rpm when being stirred operation.
In a wherein embodiment, made by the way of being gradually added dropwise when calcium carbonate slurry being added into mixed waste liquor
The spilling of slurry and waste liquid must be reacted uniformly and prevent, the charging rate of calcium carbonate slurry is 1Kg/min~20Kg/min.
In a wherein embodiment, carrying out temperature when 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 highly basic adjusting reaction solution is added 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, introduces other cations 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%.
It is that 5~8 can enable acetic acid and nitric acid in waste liquid that highly basic is added into reaction solution and adjusts the pH value of reaction solution
Enough sufficiently reactions.
S140, reaction solution is filtered to obtain filtrate.
In a wherein embodiment, reaction solution is filtered to remove the insoluble matter in reaction solution.Further,
First it will be filtered to obtain filtrate again after reaction solution stewing process 0.5h~1h.
S150, Ca-Acetate crystals and mother liquor are obtained by filtration 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
Row, the temperature of heating are 80 DEG C~100 DEG C.
In a wherein embodiment, the specific gravity for carrying out heating evaporation crystallization treatment to obtained mother liquor to filtrate is
1.31~1.36.When the concentration of calcium nitrate in mother liquor is lower, the specific gravity of mother liquor is between 1.19~1.31；And in mother liquor
The concentration of calcium nitrate increases, and the concentration of mother liquor increases to 1.31~1.36, at this point, calcium nitrate progressivelyes reach or close to full in mother liquor
With.
In a wherein embodiment, the specific gravity for carrying out heating evaporation crystallization treatment to obtained mother liquor to filtrate is
1.31~1.36 the step of specifically: continue the specific gravity of heating evaporation crystallization treatment to mother liquor after merging mother liquor with filtrate
It is 1.31~1.36.
S160, Ca-Acetate crystals are rinsed using 70 DEG C~80 DEG C of water.
In a wherein embodiment, recycles and rinse 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, Ca-Acetate crystals are dried.
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, calcium nitrate crystal is obtained by filtration after mother liquor is carried out crystallisation by cooling processing.
In a wherein embodiment, crystallisation by cooling processing the step of specifically: by mother liquor slow cooling to 10 DEG C~
25 DEG C are precipitated calcium nitrate crystal.
In a wherein embodiment, the time for carrying out crystallisation by cooling processing is 1h~20h.
In a wherein embodiment, mother liquor is filtered after the precipitation of calcium nitrate crystal to obtain calcium nitrate crystalline substance
Body and supernatant.
In a wherein embodiment, continue after obtained supernatant is merged with 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, calcium nitrate crystal is rinsed using 20 DEG C~25 DEG C of water.
In a wherein embodiment, recycles and rinse 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 filtrate containing calcium acetate and calcium nitrate is obtained by filtration after for 5~8 acetic acid and nitric acid sufficiently being reacted in the pH value of reaction solution, and
It carries out heating evaporation crystallization treatment first to obtain Ca-Acetate crystals, then carries out crystallisation by cooling and handle to obtain calcium nitrate crystal, thus
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 simple process is not needed to be extracted or be distilled, and low energy consumption, and cost recovery is low, and can be simultaneously 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 to dispersion in the water of 800L and forms calcium carbonate
Slurry.
(2) it under the speed of agitator of 100rpm, 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 gas and overflows to obtain reaction solution.Wherein, acetic acid contains in mixed waste liquor
Amount is 23%, and 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) calcium hydroxide aqueous solution that the mass concentration that 5Kg is added into reaction solution is 10% adjusts the pH value of reaction solution
It is 8.
(4) it after reaction solution being stood 0.5h carries out that filtrate is obtained by filtration.
(5) under the absolute pressure of 100KPa, filtrate, which is heated to 80 DEG C of progress heating evaporation crystallization treatment to specific gravity, 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 it repeats 23 specific gravity to mother liquor and makes the calcium nitrate in mother liquor reach or approach saturation for 1.36.
(6) obtained Ca-Acetate crystals are rinsed using 80 DEG C of the hot water of 20Kg, the flushing liquor that recycling is obtained
It is mixed with filtrate obtained in step (4) and continues 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) by specific gravity be 1.36 mother liquor slow cooling to 10 DEG C of progresss crystallisation by cooling processing so that calcium nitrate crystal analysis
Out, calcium nitrate crystal and supernatant is obtained by filtration；Supernatant is merged with 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, the flushing liquor that recycling is obtained with
The mixing of filtrate obtained in step (4) continues heating evaporation crystallization treatment, and obtained calcium nitrate crystal is placed at 30 DEG C
It carries out vacuum drying treatment and obtains 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 99% or more.
Embodiment 2
(1) under the speed of agitator of 80rpm, the calcium carbonate of 310Kg is added to dispersion in the water of 950L and forms calcium carbonate
Slurry.
(2) it under the speed of agitator of 100rpm, 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 gas and overflows to obtain reaction solution.Wherein, acetic acid contains in mixed waste liquor
Amount is 30%, and 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) calcium hydroxide aqueous solution that the mass concentration that 20Kg is added into reaction solution is 1.5% adjusts the pH of reaction solution
Value is 6.
(4) it after reaction solution being stood 1h carries out that filtrate is obtained by filtration.
(5) under the absolute pressure of 90KPa, filtrate, which is heated to 100 DEG C of progress heating evaporation crystallization treatment to specific gravity, 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 it repeats 26 specific gravity to mother liquor and makes the calcium nitrate in mother liquor reach or approach saturation for 1.31.
(6) obtained Ca-Acetate crystals are rinsed using 70 DEG C of the hot water of 30Kg, the flushing liquor that recycling is obtained
It is mixed with filtrate obtained in step (4) and continues 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) by specific gravity be 1.31 mother liquor slow cooling to 25 DEG C of progresss crystallisation by cooling processing so that calcium nitrate crystal analysis
Out, calcium nitrate crystal and supernatant is obtained by filtration；Supernatant is merged with 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, the flushing liquor that recycling is obtained with
The mixing of filtrate obtained in step (4) continues heating evaporation crystallization treatment, and obtained calcium nitrate crystal is placed at 30 DEG C
It carries out vacuum drying treatment and obtains 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 99% or more.
Embodiment 3
(1) under the speed of agitator of 50rpm, the calcium carbonate of 150Kg is added to dispersion in the water of 600L and forms 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 gas and overflows to obtain reaction solution.Wherein, in mixed waste liquor acetic acid content
It is 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) calcium hydroxide aqueous solution that the mass concentration that 3Kg is added into reaction solution is 20% adjusts the pH value of reaction solution
It is 8.
(4) it after reaction solution being stood 0.5h carries out that filtrate is obtained by filtration.
(5) under the absolute pressure of 100KPa, filtrate, which is heated to 80 DEG C of progress heating evaporation crystallization treatment to specific gravity, 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 it is repeated 12 times to the specific gravity of mother liquor and makes the calcium nitrate in mother liquor reach or approach saturation for 1.36.
(6) obtained Ca-Acetate crystals are rinsed using 80 DEG C of the hot water of 20Kg, the flushing liquor that recycling is obtained
It is mixed with filtrate obtained in step (4) and continues 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) by specific gravity be 1.36 mother liquor slow cooling to 10 DEG C of progresss crystallisation by cooling processing so that calcium nitrate crystal analysis
Out, calcium nitrate crystal and supernatant is obtained by filtration；Supernatant is merged with 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, the flushing liquor that recycling is obtained with
The mixing of filtrate obtained in step (4) continues heating evaporation crystallization treatment, and obtained calcium nitrate crystal is placed at 30 DEG C
It carries out vacuum drying treatment and obtains 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 99% or more.
Embodiment 4
(1) under the speed of agitator of 150rpm, the calcium carbonate of 280Kg is added to dispersion in the water of 1200L and forms carbonic acid
Calcium slurry.
(2) it under the speed of agitator of 300rpm, 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 gas and overflows to obtain reaction solution.Wherein, acetic acid contains in mixed waste liquor
Amount is 30%, and 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) calcium hydroxide aqueous solution that the mass concentration that 30Kg is added into reaction solution is 11% adjusts the pH value of reaction solution
It is 8.
(4) it after reaction solution being stood 0.5h carries out that filtrate is obtained by filtration.
(5) under the absolute pressure of 100KPa, filtrate, which is heated to 80 DEG C of progress heating evaporation crystallization treatment to specific gravity, 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 it repeats 33 specific gravity to mother liquor and makes the calcium nitrate in mother liquor reach or approach saturation for 1.36.
(6) obtained Ca-Acetate crystals are rinsed using 80 DEG C of the hot water of 20Kg, the flushing liquor that recycling is obtained
It is mixed with filtrate obtained in step (4) and continues 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) by specific gravity be 1.36 mother liquor slow cooling to 10 DEG C of progresss crystallisation by cooling processing so that calcium nitrate crystal analysis
Out, calcium nitrate crystal and supernatant is obtained by filtration；Supernatant is merged with 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, the flushing liquor that recycling is obtained with
The mixing of filtrate obtained in step (4) continues heating evaporation crystallization treatment, and obtained calcium nitrate crystal is placed at 30 DEG C
It carries out vacuum drying treatment and obtains 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 99% or more.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies 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, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of recovery method of mixed waste liquor, acetic acid content is 10%~30% in the mixed waste liquor, nitric acid content 1%
~8%, remaining is water, which comprises the following steps:
Calcium carbonate slurry progress neutralization reaction to no carbon dioxide gas is added into the mixed waste liquor to overflow to obtain reaction solution；
It is 5~8 that highly basic is added into the reaction solution and adjusts the pH value of the reaction solution；
It is filtered the reaction solution to obtain filtrate；
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, which is characterized in that be added described into mixed waste liquor
Calcium carbonate slurry carries out before neutralization reaction to no carbon dioxide gas overflows the step of obtaining reaction solution further including preparing the carbon
The step of sour calcium slurry:
Under agitation, calcium carbonate is added to the water dispersion and forms 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, which is characterized 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, which is characterized 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, which is characterized in that the heating evaporation crystallization treatment is
It 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, which is characterized in that carry out heating evaporation to the filtrate
The specific gravity 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, which is characterized in that described to be heated to the filtrate
Evaporative crystallization handle to the obtained mother liquor specific gravity be 1.31~1.36 the step of specifically: by the mother liquor and the filter
Liquid continues heating evaporation crystallization treatment to the specific gravity of the mother liquor after merging be 1.31~1.36.
8. the recovery method of mixed waste liquor according to claim 1, which is characterized in that described to be heated to the filtrate
The water using 70 DEG C~80 DEG C is further comprised the steps of: after the step of Ca-Acetate crystals and mother liquor is obtained by filtration after evaporative crystallization processing
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, which is characterized in that the step of crystallisation by cooling is handled
Specifically: the calcium nitrate crystal is precipitated to 10 DEG C~25 DEG C the mother liquor slow cooling.
10. the recovery method of mixed waste liquor according to claim 1, which is characterized in that described cold to mother liquor progress
But the water using 20 DEG C~25 DEG C is further comprised the steps of: to the nitre after the step of calcium nitrate crystal is obtained by filtration after crystallization treatment
Sour calcium crystal is rinsed.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB883493A (en) * | 1958-04-25 | 1961-11-29 | Escambia Chem Corp | Method for the recovery of nitrogen values and acetic acid from mixtures containing nitric and acetic acids |
| CN1183381A (en) * | 1996-11-25 | 1998-06-03 | 孙钧儒 | Method for producing gypsum, table salt and magnesium chloride from calcium-cantg. waste liquid and high- and low-temp. salt |
| CN102153187A (en) * | 2011-05-11 | 2011-08-17 | 天津理工大学 | Method for removing trace chromium in aqueous solution |
| CN103011447A (en) * | 2012-11-28 | 2013-04-03 | 浙江和鼎铜业有限公司 | Recycling and treating method of sulfuric acid waste sewage |
| CN104387256A (en) * | 2014-11-12 | 2015-03-04 | 天津渤化永利化工股份有限公司 | Method for utilizing mixed waste acids in acetic acid production device |
-
2017
- 2017-12-01 CN CN201711250684.0A patent/CN107986315B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB883493A (en) * | 1958-04-25 | 1961-11-29 | Escambia Chem Corp | Method for the recovery of nitrogen values and acetic acid from mixtures containing nitric and acetic acids |
| CN1183381A (en) * | 1996-11-25 | 1998-06-03 | 孙钧儒 | Method for producing gypsum, table salt and magnesium chloride from calcium-cantg. waste liquid and high- and low-temp. salt |
| CN102153187A (en) * | 2011-05-11 | 2011-08-17 | 天津理工大学 | Method for removing trace chromium in aqueous solution |
| CN103011447A (en) * | 2012-11-28 | 2013-04-03 | 浙江和鼎铜业有限公司 | Recycling and treating method of sulfuric acid waste sewage |
| CN104387256A (en) * | 2014-11-12 | 2015-03-04 | 天津渤化永利化工股份有限公司 | Method for utilizing mixed waste acids in acetic acid production device |
Non-Patent Citations (1)
| Title |
|---|
| 从电子加工行业产生的混合废酸中回收乙酸的方法和机理研究;倪冲;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20140515(第05期);第16,54页 * |
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