CN112279232A - Method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from production wastewater of cedryl methyl ketone - Google Patents
Method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from production wastewater of cedryl methyl ketone Download PDFInfo
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- CN112279232A CN112279232A CN202011196068.3A CN202011196068A CN112279232A CN 112279232 A CN112279232 A CN 112279232A CN 202011196068 A CN202011196068 A CN 202011196068A CN 112279232 A CN112279232 A CN 112279232A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
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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
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/48—Solid fuels essentially based on materials of non-mineral origin on industrial residues and waste materials
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention relates to the field of fine chemical engineering waste resource recycling, and particularly discloses a method for recycling and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from production wastewater of cedryl methyl ketone. The recovery preparation method comprises the following steps: s1, recycling the production wastewater through negative pressure fractionation to obtain acetic acid, and reacting the acetic acid with soda ash to obtain a sodium acetate trihydrate product; s2, adding potassium hydroxide into the wastewater after acetic acid is recycled by fractionation, neutralizing phosphoric acid in the wastewater, and dehydrating and carbonizing cedar wood oil in the wastewater into carbonized oil residue; s3, filtering and separating to obtain carbonized oil residue; s4, concentrating, cooling, crystallizing, filtering and drying the solution after filtering and separating the carbonized oil residue to obtain the monopotassium phosphate solid. According to the method, the phosphoric acid component contained in the production wastewater of the methyl cedryl ketone is recycled for preparing the potassium dihydrogen phosphate, and the acetic acid component contained in the wastewater is recycled for preparing the sodium acetate trihydrate, so that the waste is changed into valuable, the waste resources are fully utilized, and the ecological environment is effectively protected.
Description
Technical Field
The invention belongs to the field of fine chemical engineering waste resource recycling, and particularly relates to a method for recycling and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from production wastewater of cedryl methyl ketone.
Background
The methyl cedryl ketone belongs to one of natural perfume, is mainly used as raw material of perfume essence cosmetics, and the existing main preparation method adopts chemical synthesis method to produce, i.e. cedryl oil obtained by extracting cedar tree is used as main raw material, acetic anhydride and phosphorus pentoxide are added, and then the raw material is heated, catalyzed, reacted and synthesized, and the product is fractionated to obtain crude methyl cedryl ketone product, and the crude product is rectified to obtain refined methyl cedryl ketone. In the process of producing the methyl cedryl ketone, a large amount of acidic waste water is generated in the water washing process, the appearance of the acidic waste water is a black liquid with strong sour taste, the acidic waste water contains a large amount of phosphoric acid, a large amount of acetic acid and a small amount of floating oil, and the main component of the floating oil is cedar oil. If the wastewater is directly discharged into a sewage treatment system without being recycled, not only is a great deal of phosphoric acid and acetic acid resources in the wastewater wasted, but also the acidic wastewater contains a great deal of organic matters, the COD index reaches millions, and the degradation treatment is difficult, so that the overload operation of the sewage treatment system is caused, and the discharge standard is difficult to reach. If the environmental protection processing intermediary company with qualified capability assists the enterprise processing, the cost is very high, and the economic pressure of the production enterprise is also high.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects and the defects of the resource substance recovery technology in the wastewater generated in the production process of the existing methyl cedryl ketone, the method for recovering and preparing the potassium dihydrogen phosphate and the sodium acetate trihydrate from the production wastewater of the methyl cedryl ketone is provided. Namely, phosphoric acid components contained in the wastewater are recycled for preparing monopotassium phosphate, acetic acid components contained in the wastewater are recycled for preparing sodium acetate trihydrate, so that the waste is changed into valuable, waste resources are fully utilized, and the ecological environment is effectively protected.
The invention adopts the following technical scheme to achieve the purpose of the invention.
A method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from production wastewater of cedryl methyl ketone comprises the following steps:
s1, negative pressure fractionation: the production wastewater is subjected to negative pressure fractionation and recovery to obtain acetic acid, the acetic acid reacts with sodium carbonate to obtain a sodium acetate trihydrate product, and the wastewater after the acetic acid is fractionated and recovered enters the step S2;
s2, adding potassium hydroxide for treatment: and (3) adding potassium hydroxide into the wastewater obtained after the acetic acid is fractionated and recycled in the step S1, neutralizing phosphoric acid in the wastewater, and simultaneously generating high temperature due to the release of a large amount of heat when the potassium hydroxide is added for neutralization, wherein the high temperature enables the cedar wood oil to be dehydrated and carbonized to generate carbonized oil residue solid matters to float on the upper layer of the wastewater.
S3, filtering out carbonized oil residue: filtering and separating the wastewater subjected to neutralization reaction treatment by adding potassium hydroxide in the step S2 to remove carbonized oil residues, and feeding the solution subjected to filtration of the carbonized oil residues into the step S4;
s4, concentration and crystallization: concentrating, cooling, crystallizing, filtering and drying the solution obtained after the carbonized oil residue is filtered in the step S3 to obtain monopotassium phosphate solid; and (3) recycling the mother liquor obtained after the potassium dihydrogen phosphate crystallization and suction filtration in the step of recovering S1 from the next batch of wastewater for reuse.
Further, the negative pressure fractionation in step S1 is: the fractionation pressure is controlled between-0.07 MPa and-0.09 MPa, and the fractionation temperature is controlled between 60 ℃ and 100 ℃.
Further, the reaction of acetic acid and soda ash in step S1 is: heating to 50-70 deg.C, adjusting pH to 6.8-7.5, concentrating the reacted solution to obtain 25-27 Baume saturated solution, filtering to remove impurities, cooling to below 30 deg.C to crystallize and separate out sodium acetate trihydrate, and vacuum filtering and spin-drying to obtain sodium acetate trihydrate product.
Further, the sodium acetate trihydrate described in the step S1 is used for sewage treatment, pharmaceutical chemicals and printing and dyeing auxiliaries.
Further, the potassium hydroxide in step S2 is a solid or a concentrated solution of potassium hydroxide with a mass percent of more than 45%. The solid or concentrated solution of potassium hydroxide is used instead of the dilute solution of potassium hydroxide, and the main reasons are two reasons: firstly, neutralization reaction can be intensively released and heated, thereby being beneficial to the dehydration and carbonization of the cedar oil in the wastewater to generate carbonized oil residue which is easily filtered; and secondly, the extra addition of solvent (water) is reduced as much as possible, which is beneficial to neutralizing the generated potassium dihydrogen phosphate solution to form saturated solution after concentration, and energy sources for heating and concentrating can be obviously saved. In addition, the solid or concentrated solution of potassium hydroxide is adopted, and sodium hydroxide, soda ash, ammonia water and other substances are not used for neutralization treatment, and the main reason is that phosphoric acid in the wastewater is subjected to neutralization reaction with the solid or concentrated solution of sodium hydroxide, the solid or concentrated solution of soda ash, the ammonia water and the like, so that the temperature is not increased by intense heat release, the cedar wood oil contained in the wastewater is difficult to dehydrate and carbonize to generate carbonized oil residue, and the cedar wood oil in the wastewater cannot be removed through subsequent simple filtering operation. In addition, the reason why the potassium hydroxide is used for neutralization treatment without other alkali liquor is that the potassium dihydrogen phosphate obtained by neutralization treatment with the potassium hydroxide has high economic value, and the potassium dihydrogen phosphate is a valuable chemical fertilizer and a common industrial raw material.
Further, the neutralization treatment in step S2 is performed in a normal-pressure open container equipped with a bottom vent pipe, without additional heating, and the added potassium hydroxide is controlled to pH 4.3-4.8; wherein the added potassium hydroxide is controlled to pH4.5-4.6 which is the most preferable pH value, and the preferable pH value is 4.5-4.6, the phosphoric acid in the wastewater and the added potassium hydroxide just completely react, the phosphoric acid recovery rate in the wastewater can be maximized, and the added potassium hydroxide can not be wasted due to excess. High-pressure air is introduced through the vent pipe at the bottom, so that the liquid can roll uniformly to promote reaction, phosphoric acid in the wastewater and added potassium hydroxide can be quickly neutralized, and the cedar wood oil in the wastewater can be quickly dehydrated and carbonized into carbonized oil residue to float on the liquid surface, thereby being beneficial to filtering the carbonized oil residue. A large-capacity normal-pressure open container is adopted for neutralization treatment, so that supervision and capital investment of the pressure container are saved, and safety is guaranteed; in addition, the normal-pressure open container is convenient to adopt large capacity and large volume, so that the neutralization treatment batch is reduced, the product quality is favorably stabilized, and the production efficiency is favorably improved. Compared with the neutralization treatment by adopting a small-volume closed reaction kettle capable of being pressurized and heated, the neutralization treatment by adopting a large-capacity normal-pressure open container can improve the product quality and the production efficiency by more than 5 times.
Furthermore, the bottom vent pipe is a group of porous annular pipes with downward orifices, the porous annular pipes are horizontally arranged in the normal-pressure open container 10-50cm away from the bottom, the porous annular pipes are connected with an air compressor through pipelines, and the pore diameter of each porous annular pipe is 2-20 mm. Through this porous ring form pipe for highly-compressed air spouts downwards earlier to the uncovered container bottom of ordinary pressure, returns through bottom stop again and blows to liquid upper portion, thereby drives the aeration and the stirring of liquid, and has produced better beneficial effect: firstly, the ventilation is more balanced through the porous annular pipe, so that liquid in the violent exothermic strong acid and strong base neutralization reaction in the container is not easy to spill out of the open container, and operators are safer; secondly, the method is more favorable for accelerating dehydration and carbonization of the cedar oil in the wastewater into carbonized oil residue which floats on the liquid surface, so that the cedar oil is removed more completely; thirdly, the liquid can be rolled more uniformly, the potassium hydroxide is neutralized more quickly and completely, and the recovery yield of the subsequent potassium dihydrogen phosphate product is improved, and the purity of the subsequent potassium dihydrogen phosphate product is also improved. The porous annular pipe requires that the hole opening faces downwards instead of upwards, because when the hole opening faces upwards, high-pressure air directly penetrates upwards to get away from a short circuit, not only is the ventilation uneven, but also strong acid and strong base high-temperature liquid in the container, which is in violent exothermic reaction, is easily splashed out of the open container, and the personal safety of operators cannot be guaranteed.
Further, the carbonized oil residue described in step S3 is used as fuel for brickyard, boiler, etc.
Further, the concentration in step S4 is reduced pressure concentration, and the density of the concentrated solution is controlled to be 1.65-1.75 g/ml. If the concentration is higher than 1.75 g/ml, the potassium dihydrogen phosphate solution is seriously supersaturated, so that the potassium dihydrogen phosphate can generate impurity peritectic phenomena in the cooling and crystallization process, thereby seriously reducing the product purity of the potassium dihydrogen phosphate; if the concentration is less than 1.65 g/ml, the potassium dihydrogen phosphate solution is not saturated and the potassium dihydrogen phosphate is not crystallized completely by cooling, thereby significantly reducing the crystallization yield of potassium dihydrogen phosphate.
Further, the density of the concentrated solution is preferably 1.69-1.71 g/ml, and at the preferred density, the potassium dihydrogen phosphate solution is just in a saturated state, which is beneficial to improving the crystallization yield of the potassium dihydrogen phosphate and simultaneously improving the product purity of the potassium dihydrogen phosphate.
Further, the cooling-crystallization in the step S4 is to cool the concentrated solution to a temperature of 35 to 40 ℃ and to stand it for 6 to 24 hours to sufficiently precipitate monopotassium phosphate.
Further, the monopotassium phosphate described in step S4 is used as a chemical fertilizer and/or an industrial raw material.
Has the advantages that:
(1) according to the method, the phosphoric acid component contained in the wastewater in the production process of the methyl cedryl ketone is recycled for preparing the potassium dihydrogen phosphate, and the acetic acid component contained in the wastewater is recycled for preparing the sodium acetate trihydrate, so that the waste is changed into valuable, and the waste resources are fully utilized.
(2) According to the invention, after phosphoric acid, acetic acid and cedar wood oil contained in the wastewater in the production process of methyl cedar wood ketone are recovered, potassium dihydrogen phosphate and mother liquor are obtained through concentration-cooling-crystallization-suction filtration in the step S4, the mother liquor is recycled when the next wastewater is recovered in the step S1, water in the wastewater is continuously concentrated and evaporated in the continuous recovery process, resource substances in the wastewater are completely consumed and squeezed, basically no residual wastewater enters a sewage treatment system, the operation load of the sewage treatment system is obviously reduced, and the ecological environment is effectively protected.
(3) In the step S2 of adding potassium hydroxide for neutralization treatment, potassium hydroxide solid or concentrated solution is adopted instead of dilute solution of potassium hydroxide, so that the neutralization reaction can release heat and raise temperature violently, thereby being beneficial to the dehydration and carbonization of cedar oil in wastewater to generate carbonized oil residue which is easy to filter; meanwhile, the extra addition of solvent (water) is reduced as much as possible, which is beneficial to neutralizing the generated potassium dihydrogen phosphate solution to form saturated solution through concentration, and the energy used for heating and concentrating can be obviously saved.
(4) In the step S2 of adding potassium hydroxide for neutralization treatment, the neutralization treatment is carried out in a normal-pressure open container provided with a bottom vent pipe, on one hand, high-pressure air is introduced through the bottom vent pipe to roll liquid uniformly to promote reaction, so that phosphoric acid in the wastewater and the added potassium hydroxide can be quickly neutralized, and the cedar wood oil in the wastewater can be quickly dehydrated and carbonized into carbonized oil residue to float on the liquid surface, thereby being beneficial to filtering the carbonized oil residue; on the other hand, a large-capacity normal-pressure open container is adopted for neutralization treatment, so that supervision and capital investment of the pressure container are saved, and safety is guaranteed; and the normal pressure open container is convenient to adopt large capacity and large volume, reduces the neutralization treatment batch, is beneficial to stabilizing the product quality and is also beneficial to improving the production efficiency. Compared with the neutralization treatment by adopting a small-volume closed reaction kettle capable of being pressurized and heated, the neutralization treatment by adopting a large-capacity normal-pressure open container can improve the product quality and the production efficiency by more than 5 times.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1:
taking 2 tons of the production wastewater of the methyl cedryl ketone, and recycling acetic acid and phosphoric acid, wherein the steps are as follows:
s1, negative pressure fractionation: 2 tons of the production wastewater of the methyl cedrone is put into a fractionating reaction kettle with a heating jacket of 5 cubic meters, a vacuum pump is opened, the negative pressure is controlled to be about-0.09 MPa, the wastewater is heated to about 70 ℃ by high-temperature steam through the heating jacket, and the wastewater is subjected to negative pressure fractionation, cooling and recovery to obtain 900 kilograms of acetic acid solution with the content of about 43 percent. About 1100 kg of black wastewater containing phosphoric acid and cedar oil remained after the acetic acid was recovered by fractionation was introduced into the step S2.
S2, adding potassium hydroxide for treatment: transferring about 1100 kg of black wastewater subjected to acetic acid fractionation and recovery in the step S1 to a 5 cubic meter open stainless steel tank provided with a tank bottom ventilation coil (a group of porous annular pipes with downward orifices, the aperture is 8mm and the distance from the bottom of the tank is 30cm) and electric stirring, starting an air compressor to introduce high-pressure air into the tank bottom ventilation coil and start stirring, slowly adding a potassium hydroxide concentrated solution with the mass percentage concentration of 48%, stopping adding the potassium hydroxide concentrated solution when the pH value is 4.5-4.6, discharging a large amount of heat when adding potassium hydroxide for neutralization treatment, measuring that the generated high temperature reaches 96 ℃, and dehydrating and carbonizing cedar oil contained in the wastewater to generate carbonized oil residue and floating in the upper layer of the wastewater.
S3, filtering out carbonized oil residue: and (4) adding potassium hydroxide into the wastewater treated in the step S2, filtering out carbonized oil residue through plate-frame filtration to obtain wet plate-frame solid residue-carbonized oil residue, and drying and weighing 150 kg of the wet carbonized oil residue. The solution filtered by the plate frame enters the step S4;
s4, concentration and crystallization: and (4) concentrating, cooling, crystallizing, filtering and drying the solution obtained after the filtration and separation of the carbonized oil residue in the step S3, wherein the density of the concentrated solution is controlled to be 1.71 g/ml during the pressure reduction concentration, and the concentrated solution is controlled to be cooled to about 35 ℃ during the cooling and crystallization and kept stand for 8 hours to fully separate out potassium dihydrogen phosphate. And finally, 1000 kg of potassium dihydrogen phosphate solid with the content of 98 percent is obtained. Mother liquor obtained after potassium dihydrogen phosphate crystallization and suction filtration is recycled in the step S1 of recycling the next batch of wastewater, and is not discharged to an environment-friendly treatment system for treatment, so that the operation load of a sewage treatment system is obviously reduced, and the ecological environment is effectively protected.
S5, preparing sodium acetate trihydrate: putting 900 kg of acetic acid solution with the content of about 43 percent obtained in the step S1 into a stainless steel neutralization tank with a heating jacket of 3 cubic meters, heating the solution to about 65 ℃ by using high-temperature steam, adding industrial soda ash powder to the pH value of about 7.4 under the stirring condition, concentrating the reacted sodium acetate solution under reduced pressure of about-0.09 MPa and at the temperature of about 60 ℃ to obtain saturated solution with the Baume degree of 26, cooling the saturated solution to below 30 ℃, standing the saturated solution for precipitation, and performing suction filtration and centrifugal drying to obtain 900 kg of sodium acetate trihydrate solid with the sodium acetate content of 60 percent.
The carbonized oil residue obtained in the step S3 is used as an auxiliary fuel for boiler combustion or brick firing in a brick factory; the 98 percent monopotassium phosphate solid obtained in the step S4 is used for preparing a foliar fertilizer or used as an industrial raw material; the sodium acetate trihydrate solid with the sodium acetate content of 60 percent obtained in the step S5 is used for sewage treatment or raw materials of pharmaceutical chemicals or printing and dyeing auxiliaries.
Example 2:
taking 5 tons of the production wastewater of the methyl cedryl ketone, and recycling the acetic acid and the phosphoric acid, wherein the steps are as follows:
s1, negative pressure fractionation: 5 tons of the production wastewater of the methyl cedryl ketone is put into a 10 cubic meter fractionating reaction kettle containing a heating inner coil pipe, a vacuum pump is started, the negative pressure is controlled to be about-0.08 MPa, the wastewater is heated to about 80 ℃ by high-temperature steam through the inner coil pipe, and the wastewater is subjected to negative pressure fractionation, cooling and recovery to obtain 2250 kg of acetic acid solution with the content of about 42 percent. About 2750 kg of black wastewater containing phosphoric acid and cedar oil left after the acetic acid is recovered by fractionation is introduced into S2.
S2, adding potassium hydroxide for treatment: transferring about 2750 kg of black wastewater subjected to acetic acid fractionation and recycling in the step S1 to a stainless steel tank with an opening of 5 cubic meters and provided with a tank bottom ventilation coil (a group of porous annular pipes with downward orifices, the aperture is 8mm and is 30cm away from the bottom of the container) and electric stirring, starting an air compressor to introduce high-pressure air into the tank bottom ventilation coil and start stirring, slowly adding potassium hydroxide flaky solids, stopping adding the potassium hydroxide flaky solids when the pH value is 4.5-4.6, discharging a large amount of heat when adding the potassium hydroxide for neutralization treatment, measuring that the generated high temperature reaches 98 ℃, and dehydrating and carbonizing cedar oil contained in the wastewater to generate carbonized oil residue and floating in the upper layer of the wastewater.
S3, filtering out carbonized oil residue: and (4) adding potassium hydroxide into the wastewater treated in the step S2, filtering out carbonized oil residue through plate-frame filtration to obtain wet plate-frame solid residue-carbonized oil residue, and drying and weighing 375 kg of the wet carbonized oil residue. The solution filtered by the plate frame enters the step S4;
s4, concentration and crystallization: and (4) carrying out suction filtration and separation on the solution obtained after the carbonized oil residue in the step S3, and carrying out reduced pressure concentration, cooling, crystallization, suction filtration and drying, wherein the density of the concentrated solution is controlled to be 1.70 g/ml during reduced pressure concentration, and the concentrated solution is controlled to be cooled to about 37 ℃ during cooling and crystallization and is kept stand for 16 hours to fully separate out potassium dihydrogen phosphate. 2500 kg of potassium dihydrogen phosphate solid with the content of 98 percent is finally obtained. Mother liquor obtained after potassium dihydrogen phosphate crystallization and suction filtration is recycled in the step S1 of recycling the next batch of wastewater, and is not discharged to an environment-friendly treatment system for treatment, so that the operation load of a sewage treatment system is obviously reduced, and the ecological environment is effectively protected.
S5, preparing sodium acetate trihydrate: putting 2250 kg of acetic acid solution with the content of about 42 percent obtained in the step S1 into a 10-cubic meter stainless steel neutralization tank containing a heating inner coil pipe, heating the solution to about 60 ℃ by using high-temperature steam, adding industrial soda ash powder to the pH value of about 7.2 under the stirring condition, concentrating the reacted sodium acetate solution under reduced pressure of about-0.09 MPa and at about 60 ℃ to obtain a saturated solution with the Baume degree of 26, cooling the saturated solution to below 30 ℃, standing the solution for precipitation, and performing suction filtration and centrifugal drying to obtain 2250 kg of sodium acetate trihydrate solid with the sodium acetate content of 59 percent.
The carbonized oil residue obtained in the step S3 is used as an auxiliary fuel for boiler combustion or brick firing in a brick factory; the 98 percent monopotassium phosphate solid obtained in the step S4 is used for preparing a foliar fertilizer or used as an industrial raw material; the sodium acetate trihydrate solid with the sodium acetate content of 59 percent obtained in the step S5 is used for sewage treatment or raw materials of pharmaceutical chemicals or printing and dyeing auxiliaries.
Example 3:
10 tons of methyl cedryl ketone production wastewater is taken for recycling acetic acid and phosphoric acid, and the steps are as follows:
s1, negative pressure fractionation: 10 tons of the production wastewater of the methyl cedryl ketone is put into a 20 cubic meter fractionating reaction kettle containing a heating inner coil and a heating jacket, a vacuum pump is started, the negative pressure is controlled to be about-0.07 MPa, the wastewater is heated to about 90 ℃ by using high-temperature steam through the inner coil and the heating jacket at the same time, and the wastewater is subjected to negative pressure fractionation, cooling and recovery, so that 4500 kg of acetic acid solution with the content of about 41 percent is obtained. About 5500 kg of the black wastewater containing phosphoric acid and cedar wood oil left after the acetic acid is recovered by fractionation was subjected to S2.
S2, adding potassium hydroxide for treatment: transferring about 5500 kg of black wastewater after acetic acid is fractionated and recovered in the step S1 to a 10 cubic meter open stainless steel tank provided with a tank bottom ventilation coil (a group of porous annular pipes with downward orifices, the aperture is 8mm and is 30cm away from the bottom of the container) and electric stirring, starting an air compressor to introduce high-pressure air into the tank bottom ventilation coil and start stirring, slowly adding a potassium hydroxide saturated solution with the mass percentage concentration of 52%, stopping adding the potassium hydroxide concentrated solution when the pH value is 4.5-4.6, discharging a large amount of heat when adding potassium hydroxide for neutralization treatment, measuring that the generated high temperature reaches 97 ℃, and dehydrating and carbonizing cedar oil contained in the wastewater to generate carbonized oil residue and floating in the upper layer of the wastewater.
S3, filtering out carbonized oil residue: and (4) adding potassium hydroxide into the wastewater treated in the step S2, filtering out carbonized oil residue through plate-frame filtration to obtain wet plate-frame solid residue-carbonized oil residue, and drying and weighing 750 kg of the wet carbonized oil residue. The solution filtered by the plate frame enters the step S4;
s4, concentration and crystallization: and (4) carrying out suction filtration and separation on the solution obtained after the carbonized oil residue in the step S3, and then carrying out concentration-cooling-crystallization-suction filtration-drying steps, wherein the density of the concentrated solution is controlled to be 1.69 g/ml during reduced pressure concentration, and the concentrated solution is controlled to be cooled to about 39 ℃ during cooling-crystallization and kept stand for 24 hours to fully separate out potassium dihydrogen phosphate. Finally 5000 kg of potassium dihydrogen phosphate solid with the content of 98 percent is obtained. Mother liquor obtained after potassium dihydrogen phosphate crystallization and suction filtration is recycled in the step S1 of recycling the next batch of wastewater, and is not discharged to an environment-friendly treatment system for treatment, so that the operation load of a sewage treatment system is obviously reduced, and the ecological environment is effectively protected.
S5, preparing sodium acetate trihydrate: putting 4500 kg of acetic acid solution with the content of about 41 percent obtained in the step S1 into a 10-cubic meter stainless steel neutralization tank containing a heating inner coil pipe, heating the solution to about 55 ℃ by using high-temperature steam, adding industrial soda ash powder to the pH value of about 7.0 under the stirring condition, concentrating the reacted sodium acetate solution under reduced pressure of about-0.09 MPa and at the temperature of about 60 ℃ to obtain saturated solution with the Baume degree of 26, cooling to below 30 ℃, standing for precipitation, performing suction filtration and centrifugal drying to obtain 4500 kg of sodium acetate trihydrate solid with the sodium acetate content of 58 percent.
The carbonized oil residue obtained in the step S3 is used as an auxiliary fuel for boiler combustion or brick firing in a brick factory; the 98 percent monopotassium phosphate solid obtained in the step S4 is used for preparing a foliar fertilizer or used as an industrial raw material; the sodium acetate trihydrate solid with the sodium acetate content of 58 percent obtained in the step S5 is used for sewage treatment or raw materials of pharmaceutical chemicals or printing and dyeing auxiliaries.
Comparative example 1:
taking 2 tons of the production wastewater of the methyl cedryl ketone, and recycling the acetic acid and the phosphoric acid.
S1, S2, S3, S4 and S5 are the same as those in example 1;
except that the density of the concentrate in the step of S4 was controlled to be 1.76 g/ml. 1020 kg of monopotassium phosphate solid with the content of 90 percent is finally obtained. Although the solid potassium dihydrogen phosphate was increased in weight by 20 kg, the solid potassium dihydrogen phosphate content in the solid was only 90%, which was significantly lower than 98% in example 1, compared to 1000 kg of the solid potassium dihydrogen phosphate obtained in example 1, which was 98%. The reason is that the density of the concentrated solution is 1.76 g/ml, the monopotassium phosphate in the concentrated solution is in a supersaturated state, and impurities are subjected to peritectic phenomenon in the crystallization process, so that the product purity of the monopotassium phosphate is reduced.
Comparative example 2:
taking 2 tons of the production wastewater of the methyl cedryl ketone, and recycling the acetic acid and the phosphoric acid.
S1, S2, S3, S4 and S5 are the same as those in example 1;
except that the density of the concentrate in the step of S4 was controlled to 1.64 g/ml. 520 kg of potassium dihydrogen phosphate solid with the content of 98.1 percent is finally obtained. Although the potassium dihydrogen phosphate content in the solid was slightly increased compared with 1000 kg of the 98% potassium dihydrogen phosphate solid obtained in example 1, the weight of the obtained potassium dihydrogen phosphate solid was only 520 kg, which was significantly lower than 1000 kg of example 1. The reason is that the density of the concentrated solution is 1.64 g/ml, potassium dihydrogen phosphate in the concentrated solution is far from saturation, and the potassium dihydrogen phosphate is incompletely crystallized due to cooling, so that the crystallization yield of the potassium dihydrogen phosphate is obviously reduced.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the above-described embodiments. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent alterations and modifications are intended to be included within the scope of the invention, without departing from the spirit and scope of the invention.
Claims (10)
1. A method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from production wastewater of cedryl methyl ketone is characterized by comprising the following steps:
s1, negative pressure fractionation: the production wastewater is subjected to negative pressure fractionation and recovery to obtain acetic acid, the acetic acid reacts with sodium carbonate to obtain a sodium acetate trihydrate product, and the wastewater after the acetic acid is fractionated and recovered enters the step S2;
s2, adding potassium hydroxide for treatment: adding potassium hydroxide into the wastewater obtained after the acetic acid is fractionated and recovered in the step S1, neutralizing phosphoric acid in the wastewater, and dehydrating and carbonizing the cedar wood oil in the wastewater into carbonized oil residue;
s3, filtering out carbonized oil residue: filtering and separating the wastewater subjected to neutralization reaction treatment by adding potassium hydroxide in the step S2 to remove carbonized oil residues, and feeding the solution subjected to filtration of the carbonized oil residues into the step S4;
s4, concentration and crystallization: concentrating, cooling, crystallizing, filtering and drying the solution obtained after the carbonized oil residue is filtered in the step S3 to obtain monopotassium phosphate solid; and (3) recycling the mother liquor obtained after the potassium dihydrogen phosphate crystallization and suction filtration in the step of recovering S1 from the next batch of wastewater for reuse.
2. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 1, wherein the negative pressure fractionation in step S1 is: the fractionation pressure is controlled between-0.07 MPa and-0.09 MPa, and the fractionation temperature is controlled between 60 ℃ and 100 ℃.
3. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 1, wherein the reaction of acetic acid and soda ash in step S1 is: heating to 50-70 deg.C, adjusting pH to 6.8-7.5, concentrating the reacted solution to obtain 25-27 Baume saturated solution, filtering to remove impurities, cooling to below 30 deg.C to crystallize and separate out sodium acetate trihydrate, and vacuum filtering and spin-drying to obtain sodium acetate trihydrate product.
4. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 1, wherein the method comprises the following steps: the potassium hydroxide in the step S2 is a solid or a concentrated potassium hydroxide solution with a mass percent of 45% or more.
5. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 1, wherein the method comprises the following steps: the neutralization treatment in step S2 is performed in a normal-pressure open container equipped with a bottom vent pipe, and the added potassium hydroxide is controlled to have a pH of 4.3 to 4.8.
6. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 5, wherein the method comprises the following steps: the bottom vent pipe is a group of porous annular pipes with downward orifices, the porous annular pipes are horizontally arranged in the normal-pressure open container 10-50cm away from the bottom, and the porous annular pipes are connected with an air compressor through pipelines.
7. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 1, wherein the method comprises the following steps: the concentration in the step S4 is reduced pressure concentration, and the density of the concentrated solution is controlled to be 1.65-1.75 g/ml.
8. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 7, wherein the method comprises the following steps: the density of the control concentrated solution is 1.69-1.71 g/ml.
9. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 1, wherein the method comprises the following steps: the cooling-crystallization in the step S4 is to cool the concentrated solution to the temperature of 35-40 ℃ and to stand for 6-24 hours to fully separate out the monopotassium phosphate.
10. The method for recovering and preparing potassium dihydrogen phosphate and sodium acetate trihydrate from the production wastewater of cedryl methyl ketone as claimed in claim 1, wherein the method comprises the following steps: the sodium acetate trihydrate of the step S1 is used for sewage treatment, pharmaceutical chemicals and printing and dyeing auxiliaries; the carbonized oil residue in the step S3 is used as fuel; the monopotassium phosphate described in step S4 is used as a chemical fertilizer and/or an industrial raw material.
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