CN116573744B - Method for treating industrial waste liquid - Google Patents
Method for treating industrial waste liquid Download PDFInfo
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- CN116573744B CN116573744B CN202310854004.5A CN202310854004A CN116573744B CN 116573744 B CN116573744 B CN 116573744B CN 202310854004 A CN202310854004 A CN 202310854004A CN 116573744 B CN116573744 B CN 116573744B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0004—Crystallisation cooling by heat exchange
- B01D9/0013—Crystallisation cooling by heat exchange by indirect heat exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/02—Crystallisation from solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/08—Cleaning containers, e.g. tanks
- B08B9/0804—Cleaning containers having tubular shape, e.g. casks, barrels, drums
- B08B9/0808—Cleaning containers having tubular shape, e.g. casks, barrels, drums by methods involving the use of tools, e.g. by brushes, scrapers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/249—Deacidifying or drying the crystals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D2009/0086—Processes or apparatus therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
A method for treating industrial waste liquid belongs to the technical field of industrial waste liquid treatment. The method comprises the following steps: adding ammonium bicarbonate into waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid, and regulating the pH value of the mixed solution to 2-2.2; distilling the mixed solution to obtain an acetic acid aqueous solution, and cooling to crystallize the rest mixed solution to obtain an ammonium sulfate crude product; leaching the ammonium sulfate crude product with ethanol, and centrifuging and drying to obtain wet ammonium sulfate and leaching solution; discharging the leaching solution outwards, and drying wet ammonium sulfate to obtain finished ammonium sulfate; adding water and solid sodium hydroxide into the distilled acetic acid aqueous solution, and cooling to obtain 25% sodium acetate aqueous solution. The method has simple process and strong practicability, and realizes the efficient separation and reutilization of the waste liquid after obtaining the ammonium sulfate crude product and purer acetic acid aqueous solution through reaction and distillation and further obtaining the ammonium sulfate finished product and the sodium acetate solution through treatment.
Description
Technical Field
The invention belongs to the technical field of industrial waste liquid treatment, and particularly relates to a method for treating industrial waste liquid.
Background
In the production of the liquid crystal intermediate alkyl cyclohexylphenol, it is necessary to discharge a large amount of waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid, which typically has the following composition in terms of weight ratio: 5-15% of sulfuric acid, 35-40% of acetic acid, 15-20% of ammonium persulfate and 25-30% of water, wherein the ammonium persulfate is unstable and is easy to decompose into ammonium bisulfate when meeting water. Waste acetic acid belongs to dangerous waste, has high acidity and is corrosive. With the increasing importance of environmental protection in various countries, in view of the harm of industrial waste liquid to the environment, staff and other people, the emission standard of industrial waste liquid is established at home and abroad, and the standard regulation is becoming stricter. However, a large amount of acetic acid waste liquid is still discharged directly every year without treatment, which not only causes a large amount of resource loss, but also pollutes the environment. Therefore, the acetic acid waste liquid is treated and recycled, so that the method not only has good economic benefit, but also is a production link necessary for environmental protection.
At present, the method for treating acetic acid waste liquid in the prior art comprises the following steps: the method comprises a neutralization method, an adsorption method, a synthetic acetate method, an esterification method, a membrane separation method, a rectification method, a biochemical method, a combination method and the like, but most of acetic acid waste liquid generated in the production process of the liquid crystal intermediate is not recycled, and only a mixture of various substances is obtained after preliminary alkali addition neutralization treatment, however, the mixture cannot be separated and can only be finally used as sewage to be discharged after reaching standards after being treated by the biochemical method. In terms of cost, according to preliminary statistics, thousands of yuan are consumed for treating each ton of acetic acid waste liquid. As can be seen from the analysis of the technical scheme disclosed above, the prior art method has the defects of more equipment requirements, high investment cost, strict operation requirements, large occupied area and the like.
The method treats waste acetic acid by adjusting the pH value of waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid, obtains a crude ammonium sulfate product and a purer acetic acid aqueous solution, and further obtains finished ammonium sulfate and sodium acetate solutions. The agricultural production in China has great demands on ammonium fertilizers, and the ammonium sulfate component prepared by separating from the waste liquid consisting of sulfuric acid, ammonium persulfate and acetic acid is a good fertilizer resource. Sodium acetate solution with mass concentration of 25% is widely used in the field of sewage treatment. In the aspect of national conditions of China, when treated sewage is discharged into closed water or slow-flowing water to cause eutrophication so as to influence water supply and water sources, an A2/O process (anaerobic-anoxic-aerobic biological nitrogen and phosphorus removal process) is adopted, and the process can achieve good nitrogen and phosphorus removal effects. The sodium acetate solution with the mass concentration of 25% is an important nutrient which needs to be added in the anoxic stage of the sewage A2/O treatment process.
Disclosure of Invention
The invention aims at: in order to overcome the defects of the background technology, a method for treating industrial waste liquid is provided.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method of treating industrial waste, comprising the steps of:
step 1: adding ammonium bicarbonate into waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid for reaction, stirring by a stirrer to fully mix the waste liquid with the ammonium bicarbonate, and regulating the pH value of the mixed solution to 2-2.2;
step 2: distilling the mixed solution prepared in the step 1 to obtain an acetic acid aqueous solution, and cooling to crystallize the rest mixed solution to obtain an ammonium sulfate crude product;
step 3: eluting the ammonium sulfate crude product generated in the step 2 by ethanol, and carrying out centrifugal drying on the eluted mixed solution to obtain wet ammonium sulfate and eluent;
step 4: discharging the leaching solution generated in the step 3 outwards, and drying wet ammonium sulfate to obtain finished ammonium sulfate;
step 5: adding water and solid sodium hydroxide into the acetic acid aqueous solution obtained by distillation in the step 2, and cooling by circulating water to prepare a sodium acetate aqueous solution with the mass concentration of 25%;
wherein the reactions in step 2, step 3 and step 4 are carried out in an integrated reaction apparatus; the integrated reaction equipment comprises a cleaning and drying box, wherein a distillation tower is installed at the top end of the cleaning and drying box, an annular pipe is arranged on the outer side of the cleaning and drying box, a plurality of shunt pipes penetrating into the cleaning and drying box are formed in circumferential equidistant mode on the outer wall of the annular pipe, a spray head used for spraying the cleaning and drying box is fixedly connected to the end part of each shunt pipe, a water pipe is formed on the outer wall of each annular pipe, an inductor coil in a threaded mode is installed in the cleaning and drying box, a material taking opening penetrating into an inner cavity is formed in the outer wall of the cleaning and drying box, and an arc-shaped rotating plate is connected to the material taking opening in a rotating mode through a rotating shaft; a feeding mechanism is arranged in the cleaning drying box and above the annular pipe, and the feeding mechanism is used for automatically conveying crystals;
the feeding mechanism comprises: a wall scraping assembly and a lifting assembly; the scraping wall assembly is arranged in the top end of the cleaning and drying box and is used for automatically scraping crystals and dumping the crystals; the lifting assembly is arranged below the scraping assembly and is used for shielding sprayed ethanol when the scraping assembly is used for dumping and crystallizing; the inside of washing drying cabinet just is located the below of lifting unit and is provided with centrifugal mechanism, centrifugal mechanism is used for carrying out centrifugal dehydration to the crystallization that sprays.
Preferably, in the step 1, after the waste liquid consisting of sulfuric acid, ammonium persulfate and acetic acid is reacted with ammonium bicarbonate, when the sulfuric acid and ammonium persulfate are completely reacted and the solute in the mixed solution is only acetic acid and ammonium sulfate, the pH value of the mixed solution is 2-2.2.
Preferably, the aqueous acetic acid solution obtained by distillation in the step 2 has a mass concentration of 40-50%.
Preferably, the wall scraping assembly comprises: install the driving motor at washing drying cabinet one end outer wall, the inside symmetry of wasing the drying cabinet is provided with two upset boards, two the upset board rotates with washing the drying cabinet through pivot, bearing and is connected, one the upset board passes through connecting axle and driving motor's output fixed connection, the one end outer wall that the driving motor was kept away from to the washing drying cabinet is provided with two intermeshing's first gear, two first gear pass through the connecting axle respectively with two upset board fixed connection, two the top of upset board is all moulded has the locating plate, the top of locating plate is connected with the rotation scraper blade through pivot symmetry rotation.
Preferably, the lifting assembly comprises: the first driving wheel is fixedly connected to one end of the first gear, far away from the cleaning drying box, of the first gear, the outer wall of the first driving wheel is meshed and sleeved with a synchronous belt, the inner wall of the bottom end of the synchronous belt is meshed and sleeved with a second driving wheel, one end of the second driving wheel is fixedly connected with a second gear positioned inside the cleaning drying box through the connecting shaft, the outer wall of the second gear is meshed and connected with a rack which is connected with the cleaning drying box in a vertical sliding mode, and one end of the rack is provided with a lifting baffle ring which is connected with the cleaning drying box in a vertical sliding mode.
Preferably, the centrifugal mechanism comprises: install the inside servo motor in washing the drying cabinet bottom, servo motor's output fixedly connected with drying cylinder, the drying cylinder is located the below that goes up and down to keep off the ring, take the material mouth has been seted up to the outer wall of drying cylinder, take the inside of material mouth to rotate through the pivot and be connected with arc baffle.
Preferably, the top end of the distillation tower is fixedly connected with an exhaust pipe, the outer wall of the cleaning and drying box is fixedly connected with a hot and humid air exhaust pipe, one end of the hot and humid air exhaust pipe inserted into the cleaning and drying box faces the drying cylinder, and the other end of the hot and humid air exhaust pipe is connected with an exhaust fan; the blast pipe is connected with the collection storehouse that is used for collecting acetic acid water, the bottom of distillation column is provided with the conveying pipeline that runs through to wasing the drying cabinet inside, sets up the delivery valve on the conveying pipeline.
Preferably, the water delivery pipe is connected with the water tank through a pipeline, a water pump is arranged on the pipeline, a condenser is arranged at the top end of the inner wall of the cleaning and drying box, and the induction coil and the condenser are electrically connected with an external controller through wires.
Preferably, the cleaning drying box is provided with a turnover groove for the turnover plates to turn over, the peripheral wall of the turnover plates is provided with sealing rubber strips, and when the two turnover plates are in a horizontal state, the sealing rubber strips are in sealing contact with the inner wall of the cleaning drying box; a hollow cavity is arranged in the turnover plate, and a heat preservation and insulation material is arranged in the hollow cavity; the upper surface of locating plate is provided with the recess of reverse round platform form, the lower surface of rotation scraper blade and the upper surface of locating plate coincide each other.
Preferably, a cavity for radiating is formed in the cleaning drying box and located on the outer side of the servo motor, and the outer walls of the drying cylinder and the cleaning drying box are provided with hole grooves; the outside of servo motor is provided with the drain pipe with wash the drying cabinet fixed connection, the drain pipe runs through to the outside of wasing the drying cabinet and is used for carrying out the collection box that collects to the leacheate and link to each other.
Compared with the prior art, the invention has the beneficial effects that:
1. the method has the advantages of simple process and strong practicability, waste acetic acid is treated by adjusting the pH value of waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid, the reaction principle is that weak acid is prepared by strong acid, carbonic acid is easy to decompose, new impurities are not introduced, crude ammonium sulfate and purer aqueous acetic acid solution are obtained, and finished ammonium sulfate and sodium acetate solution are further obtained, so that the method can be used as fertilizer resources and important nutritional agents which need to be added in the anoxic stage in the sewage A2/O treatment process respectively, and further comprehensive benefits can be brought.
2. The method can recycle the acetic acid and the ammonium sulfate in the waste liquid composed of the sulfuric acid, the ammonium persulfate and the acetic acid to prepare the sodium acetate solution and the ammonium sulfate finished product, and has the advantages of simple process, strong practicability, safe and stable operation and good treatment effect, and can obtain better economic benefit compared with the traditional neutralization treatment of the acetic acid by adding alkali. Moreover, the prepared product is purer, the ethanol used for leaching can be recycled, the treatment effect of the technological process is good, the cost is low, and the product is matched with a production device, so that the method has a good application prospect.
3. The integrated reaction equipment is provided with the feeding mechanism, the residual solution is led into the feeding mechanism after the acetic acid aqueous solution is evaporated by the distillation tower, the residual solution is cooled by starting the condenser to become a crystallized ammonium sulfate crude product, crystals on the outer wall of the scraping component are scraped and collected, the residual crystallization materials on the outer wall of the scraping component are reduced as much as possible, the ports of the spray heads are blocked by the lifting component, and the ethanol sprayed by the spray heads is prevented from adhering to the outer wall of the scraping component, so that the next cooling and molding crystallization is influenced. When the crystallization is not remained on the outer wall of the wall scraping assembly, the operation is reversed, so that the wall scraping assembly can be reset. Simultaneously, start the ethanol pump in the water tank and pump out, carry to the shower nozzle through raceway, ring pipe and shunt tubes, spray the ammonium sulfate crude to make leacheate and wet product ammonium sulfate separation through centrifugal mechanism, outwards discharge leacheate through the drain pipe simultaneously. And starting the induction coil to heat the interior of the cleaning and drying box, and drying the centrifuged wet ammonium sulfate to form the finished ammonium sulfate. The integrated reaction equipment integrates the functions of distillation, condensation, spraying, centrifugal drying, drying and the like, has small occupied area and exquisite and reasonable design structure, automatically connects and fuses a plurality of production procedures on one piece of equipment, and can effectively improve the production efficiency and reduce the labor intensity of workers; greatly reduces the purchase cost and the number of operators of various devices, and further reduces the production cost.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
FIG. 2 is a schematic view showing the internal structure of the washing and drying cabinet of the present invention;
FIG. 3 is a schematic diagram showing the connection structure of the washing and drying box and the centrifugal mechanism;
FIG. 4 is a schematic diagram of an exploded construction of the feed mechanism of the present invention;
FIG. 5 is a schematic view of the centrifugal mechanism of the present invention;
FIG. 6 is a schematic view of the structure of the present invention shown in FIG. 2, partially enlarged at A;
FIG. 7 is a schematic view of the structure of the present invention shown in FIG. 2 at B in a partially enlarged manner;
fig. 8 is a schematic view of the installation structure of the arc-shaped rotating plate on the material taking opening.
In the figure: 1. cleaning a drying box; 2. a feeding mechanism; 201. a driving motor; 202. rotating the scraping plate; 203. a turnover plate; 204. a first gear; 205. a first driving wheel; 206. a synchronous belt; 207. a second driving wheel; 208. a second gear; 209. a rack; 2010. lifting baffle rings; 2011. a positioning plate; 3. a centrifugal mechanism; 301. a drying cylinder; 302. a servo motor; 303. an arc baffle; 4. a distillation column; 5. a shunt; 6. a material taking port; 7. a drain pipe; 8. an inductance coil; 9. a water pipe; 10. an annular tube; 11. a hot and humid gas pipe; 12. an exhaust pipe; 13. an arc rotating plate; 14. an elastic sheet; 15. and a clamping block.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "configured" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art. Hereinafter, an embodiment of the present invention will be described in accordance with its entire structure.
Example 1
In an embodiment of the invention, a method for treating industrial waste liquid comprises the following steps:
step 1: to 100kg of a waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid, 34kg of ammonium bicarbonate was added for reaction while stirring with a stirrer to mix the waste liquid with ammonium bicarbonate sufficiently. After the waste liquid consisting of sulfuric acid, ammonium persulfate and acetic acid reacts with ammonium bicarbonate, when the sulfuric acid and the ammonium persulfate completely react and the solute in the mixed solution is only acetic acid and ammonium sulfate, the pH value of the mixed solution is 2-2.2.
The main reaction formula of ammonium bicarbonate is as follows:
2NH 4 HCO 3 +H 2 SO 4 =(NH 4 ) 2 SO 4 +2CO 2 ↑+2H 2 O；
NH 4 HCO 3 +NH 4 HSO 4 =(NH 4 ) 2 SO 4 +CO 2 ↑+H 2 O。
step 2: and (3) distilling the mixed solution prepared in the step (1) at 100-110 ℃ to obtain 60kg of acetic acid aqueous solution with the mass concentration of 40%. Cooling to crystallize the mixed solution to obtain 50kg of ammonium sulfate crude product.
Step 3: and (3) leaching the ammonium sulfate crude product generated in the step (2) by using ethanol, and carrying out centrifugal drying on the leached mixed solution to obtain 50kg of wet ammonium sulfate and leaching liquor.
Step 4: and (3) discharging the leaching solution generated in the step (3) outwards, and drying the wet ammonium sulfate to obtain 48kg of finished ammonium sulfate.
Step 5: adding 59kg of water and 16kg of solid sodium hydroxide into the acetic acid aqueous solution obtained by distillation in the step 2, and cooling by circulating water to prepare the sodium acetate aqueous solution with the mass concentration of 25%.
The reaction for producing sodium acetate is as follows:
CH 3 COOH+NaOH=CH 3 COONa+H 2 O。
wherein the reactions in step 2, step 3 and step 4 are carried out in an integrated reaction apparatus.
Referring to fig. 1-8, the integrated reaction apparatus includes a cleaning and drying box 1 with a distillation tower 4 installed at the top end, an annular pipe 10 is disposed at the outer side of the cleaning and drying box 1, a plurality of shunt pipes 5 penetrating into the cleaning and drying box 1 are circumferentially and equidistantly formed on the outer wall of the annular pipe 10, a nozzle for spraying the cleaning and drying box 1 is fixedly connected to the end of the shunt pipes 5, a water pipe 9 is formed on the outer wall of the annular pipe 10, a threaded inductance coil 8 is installed in the cleaning and drying box 1, a material taking opening 6 penetrating into an inner cavity is formed on the outer wall of the cleaning and drying box 1, an arc-shaped rotating plate 13 is rotatably connected to the inner side of the material taking opening 6 through a rotating shaft, an exhaust pipe 12 is fixedly connected to the top end of the distillation tower 4, a hot and humid air exhaust pipe 11 is fixedly connected to the outer wall of the cleaning and drying box 1, one end of the hot and humid air exhaust pipe 11 inserted into the cleaning and drying box 1 faces a drying cylinder 301, and the other end of the hot and humid air exhaust pipe 11 is connected with an exhaust fan; the blast pipe 12 is connected with the collection storehouse that is used for collecting acetic acid water, the bottom of distillation column 4 is provided with the conveying pipeline that runs through to wasing inside the drying cabinet 1, sets up the delivery valve on the conveying pipeline. The water pipe 9 is connected with the output of water pump, and the water pump passes through the pipeline to be connected with the water tank, washs the inner wall top of drying cabinet 1 and installs the condenser, and inductor 8, condenser all pass through wire and external controller electric connection, washs the inside of drying cabinet 1 and be located the top of ring pipe 10 and be provided with feeding mechanism 2, and feeding mechanism 2 is used for carrying out automatic transport to the crystallization.
The feeding mechanism 2 comprises: a wall scraping assembly and a lifting assembly; the scraping wall assembly is arranged in the top end of the cleaning and drying box 1 and is used for automatically scraping crystals and dumping the crystals; the lifting assembly is arranged below the scraping assembly and is used for shielding sprayed ethanol when the scraping assembly is used for dumping and crystallizing; the inside of the cleaning and drying box 1 and the lower part of the lifting component are provided with a centrifugal mechanism 3, and the centrifugal mechanism 3 is used for centrifugally dewatering the sprayed crystals.
The centrifugal mechanism 3 comprises: install the servo motor 302 inside washing drying cabinet 1 bottom, servo motor 302's output fixedly connected with drying cylinder 301, drying cylinder 301 is located the below that goes up and down to keep off ring 2010, and the material mouth has been seted up to drying cylinder 301's outer wall, and the inside of taking the material mouth is connected with arc baffle 303 through the pivot rotation, and servo motor 302's outside is provided with the drain pipe 7 with washing drying cabinet 1 fixed connection, and drain pipe 7 runs through to washing drying cabinet 1's outside and is used for carrying out the collection box that collects to the leacheate and link to each other.
In this embodiment: when the device is used, the reacted waste liquid is distilled through the distillation tower 4, acetic acid steam generated by distillation is led to the collecting bin through the exhaust pipe 12 to be condensed and collected, then the residual ammonium sulfate solution in the distillation tower 4 is discharged to the inside of the cleaning and drying box 1 through a pipeline and is contacted with the outer wall of the scraping wall assembly, meanwhile, the overflow of the acetic acid aqueous solution is avoided through the sealing rubber strip, and then the condenser is started to cool the acetic acid aqueous solution in the cleaning and drying box 1 through the external controller, so that the solution can be cooled to form crystalline ammonium sulfate crude products.
Meanwhile, through the scraping wall component, the lifting component can scrape crystals on the outer wall of the scraping wall component, so that the crystals are effectively prevented from remaining on the outer wall of the scraping wall component, ports of a plurality of spray heads are blocked through the lifting component, and the spray heads are prevented from adhering to the outer wall of the scraping wall component, so that the next cooling and molding crystals are influenced.
When the crystallization is not remained on the outer wall of the wall scraping assembly basically, the operation is reversed, so that the wall scraping assembly can be reset, and the ammonium sulfate solution generated after the distillation in the distillation tower 4 is cooled in the process. Simultaneously, the water pump is started to spray ethanol in the water tank to the inside of the cleaning and drying box 1 through the water pipe 9, the annular pipe 10, the shunt pipe 5 and the spray head, at the moment, the crude ammonium sulfate product in the drying cylinder 301 forms wet ammonium sulfate under the spraying of ethanol, meanwhile, the servo motor 302 is started to drive the drying cylinder 301 to rotate, at the moment, the wet ammonium sulfate in the drying cylinder 301 separates leacheate and wet ammonium sulfate from each other under the centrifugal action of the drying cylinder 301 through a hole groove in the drying cylinder 301, the leacheate can be discharged outwards through the water drain pipe 7, then the induction coil 8 is started to heat the inside of the cleaning and drying box 1 through the external controller, the centrifuged wet ammonium sulfate can be dried, at the moment, the exhaust fan connected with the wet and hot air exhaust pipe 11 can be started, the wet and hot air generated by drying is discharged from the device through the wet and hot air exhaust pipe 11, and the improvement of drying efficiency is promoted. And after the drying operation is finished, obtaining the finished product ammonium sulfate.
The arc-shaped rotating plate 13 and the arc-shaped baffle 303 are respectively connected with the cleaning drying box 1 and the drying cylinder 301 in a clamping way through the clamping components, then the arc-shaped rotating plate 13 and the arc-shaped baffle 303 are sequentially rotated by taking the rotating shaft as the axis, and at the moment, the clamping block 15 extrudes the elastic piece 14 under the extrusion of external force, so that the arc-shaped rotating plate 13 and the arc-shaped baffle 303 are outwards rotated and opened, and the finished product ammonium sulfate inside the drying cylinder 301 can be taken out. After the arc-shaped rotating plate 13 and the arc-shaped baffle 303 are respectively clamped and connected with the cleaning and drying box 1 and the drying cylinder 301 through the clamping assembly, the next crystallization can be sprayed and dried, and therefore the aim of improving the production efficiency of ammonium sulfate is fulfilled.
As a preferred embodiment of the present invention, the wall scraping assembly includes: install the driving motor 201 at the outer wall of washing drying cabinet 1 one end, the inside symmetry of wasing drying cabinet 1 is provided with two upset boards 203, two upset boards 203 are connected through pivot, bearing and washing drying cabinet 1 rotation, one upset board 203 is through connecting axle and driving motor 201's output fixed connection, washing drying cabinet 1 is kept away from driving motor 201's one end outer wall and is provided with two intermeshing's first gear 204, two first gears 204 pass through the connecting axle respectively with two upset boards 203 fixed connection, the top of two upset boards 203 all forms locating plate 2011, the top of locating plate 2011 is connected with rotation scraper blade 202 through pivot symmetry rotation.
The lifting assembly comprises: the first driving wheel 205 is fixedly connected to one end, far away from the cleaning and drying box 1, of the first gear 204 through a connecting shaft, the outer wall of the first driving wheel 205 is in meshed connection with the synchronous belt 206, the inner wall of the bottom end of the synchronous belt 206 is in meshed connection with the second driving wheel 207, one end of the second driving wheel 207 is fixedly connected with the second gear 208 positioned inside the cleaning and drying box 1 through the connecting shaft, the outer wall of the second gear 208 is in meshed connection with the rack 209 which is in up-down sliding connection with the cleaning and drying box 1, and one end of the rack 209 is provided with the lifting baffle ring 2010 which is in up-down sliding connection with the cleaning and drying box 1.
In this embodiment: one overturning plate 203 is driven to rotate by starting the driving motor 201, meanwhile, one first gear 204 is driven by one overturning plate 203 to drive the other overturning plate 203 to rotate through mutual engagement with the other first gear 204, and meanwhile, the positioning plate 2011 is driven by the overturning plate 203 to synchronously rotate.
In this process, the rotating scraper 202 rotates with the rotation shaft as the axis along with the rotation of the overturning plate 203 and the positioning plate 2011, and meanwhile, by setting the weight of the rotating end of the rotating scraper 202 to be greater than one end of the rotation axis, the rotating scraper 202 can rotate along the outer walls of the overturning plate 203 and the positioning plate 2011 under the guidance of the outer walls of the positioning plate 2011, so that crystals on the upper surfaces of the overturning plate 203 and the positioning plate 2011 can drop into the drying cylinder 301, and meanwhile, the crystals on the outer walls of the overturning plate 203 and the positioning plate 2011 can be scraped through the rotating scraper 202, and the crystals are effectively prevented from remaining on the outer walls of the overturning plate 203 and the positioning plate 2011.
Meanwhile, the first driving wheel 205 drives the second driving wheel 207 to rotate through the synchronous belt 206 under the driving of the first gear 204, meanwhile, the second gear 208 drives the rack 209 to descend through meshing under the driving of the second driving wheel 207, and at the moment, the lifting baffle ring 2010 slides down along the inner wall of the cleaning drying box 1 under the driving of the rack 209 until the outer wall of the lifting baffle ring 2010 blocks the ports of a plurality of spray heads, so that the ethanol sprayed out of the spray heads is prevented from adhering to the outer walls of the overturning plate 203 and the positioning plate 2011.
As a preferred embodiment of the invention, a turnover groove for the turnover plates 203 to turn over is formed in the cleaning and drying box 1, and sealing rubber strips are arranged on the peripheral walls of the turnover plates 203, when the two turnover plates 203 are in a horizontal state, the sealing rubber strips are in sealing contact with the inner wall of the cleaning and drying box 1, so that the situation of liquid overflow is prevented; a hollow cavity is arranged in the turnover plate 203, and a heat preservation and insulation material is arranged in the hollow cavity, so that the influence of the drying heat below on the condensation operation above can be prevented; the upper surface of the positioning plate 2011 is provided with an inverted circular truncated cone-shaped groove, and the lower surface of the rotating scraper 202 is mutually matched with the upper surface of the positioning plate 2011.
In this embodiment: the outer wall of the round table shape is matched with the outer wall of the rotating scraper 202, and the rotating end of the rotating scraper 202 is heavier than the end rotationally connected with the positioning plate 2011, so that the rotating scraper 202 automatically rotates by taking the rotating shaft as the axis under the self weight in the rotating process of the positioning plate 2011.
As a preferred embodiment of the present invention, a cavity for heat dissipation is formed inside the cleaning and drying box 1 and outside the servo motor 302, and both the drying cylinder 301 and the outer wall of the cleaning and drying box 1 are provided with holes and grooves.
In this embodiment: the servo motor 302 can be subjected to heat dissipation operation in the use process through the mutual matching of the cavity and the hole groove.
The working principle of the invention is as follows: the reacted waste liquid is distilled through the distillation tower 4, acetic acid steam generated by distillation is led to a collecting bin through an exhaust pipe 12 for condensation and collection, and then the residual ammonium sulfate solution in the distillation tower 4 is discharged to the inside of the cleaning and drying box 1 through a pipeline and is contacted with the upper surfaces of the positioning plate 2011 and the overturning plate 203, and meanwhile, the sealing rubber strips on the periphery of the overturning plate 203 can avoid the solution from overflowing to the lower part.
Then, the condenser is started by an external controller to cool the ammonium sulfate solution in the cleaning and drying box 1 to form a crystalline ammonium sulfate crude product (the optimal temperature of ammonium sulfate crystallization is 40-42 ℃), then, the driving motor 201 is started to drive one turnover plate 203 to rotate, and simultaneously, one first gear 204 drives the other turnover plate 203 to rotate under the driving of the one turnover plate 203 through the mutual meshing with the other first gear 204, and the positioning plate 2011 synchronously rotates under the driving of the turnover plate 203.
Specific explanation is required: the end part of one end of the rotating scraper 202 far away from the rotating shaft is attached to the outer walls of the positioning plate 2011 and the overturning plate 203, the end part of the rotating scraper 202 far away from the rotating end of the rotating shaft is heavier than the end connected with the rotating shaft, and meanwhile, the outer diameter and the tooth number of the second driving wheel 207 are half of those of the first driving wheel 205.
In this process, the rotating scraper 202 rotates with the rotation of the turnover plate 203 and the positioning plate 2011 by taking the rotation shaft as the axis, and meanwhile, since the weight of the free rotating end of the rotating scraper 202 is heavier than that of the end connected to the rotation shaft, the rotating scraper 202 can rotate along the outer walls of the turnover plate 203 and the positioning plate 2011 under the guidance of the outer wall of the positioning plate 2011. When crystals on the upper surfaces of the turning plate 203 and the positioning plate 2011 fall into the drying cylinder 301, the rotary scraping plate 202 is made to scrape off crystals on the outer walls of the turning plate 203 and the positioning plate 2011, so that the amount of crystals remained on the outer walls of the turning plate 203 and the positioning plate 2011 is reduced as much as possible.
Meanwhile, the first driving wheel 205 drives the second driving wheel 207 to rotate through the synchronous belt 206 under the driving of the first gear 204, the second gear 208 drives the rack 209 to descend through meshing under the driving of the second driving wheel 207, and at the moment, the lifting baffle ring 2010 slides down along the inner wall of the cleaning drying box 1 under the driving of the rack 209 until the outer wall of the lifting baffle ring 2010 blocks the ports of all spray heads, so that the ethanol sprayed by the spray heads is prevented from being adhered to the outer walls of the overturning plate 203 and the positioning plate 2011.
When the turning plate 203 and the positioning plate 2011 are rotated to scrape the crystal on the upper surface of the turning scraper 202, the driving motor 201 drives the turning plate 203 to reverse the above operation, so that the turning plate 203 is turned and reset. In order to reset the rotating scraper 202, the two turning plates 203 are required to rotate to a horizontal state and then to turn upwards to move by an angle of 10-20 degrees, in this process, the rotating scraper 202 is guided by the positioning plate 2011 to rotate along the outer walls of the turning plates 203 and the positioning plate 2011 to reset to an initial position, and then the two turning plates 203 are required to rotate to restore to the horizontal position, so that the ammonium sulfate solution led out again in the distillation tower 4 can be subjected to cooling crystallization operation.
The water pump is started to spray the ethanol in the water tank to the inside of the cleaning and drying box 1 through the water pipe 9, the annular pipe 10, the shunt pipe 5 and the spray head, and at the moment, the crude ammonium sulfate product in the drying cylinder 301 forms wet ammonium sulfate under the spraying of the ethanol. The servo motor 302 is started to drive the drying cylinder 301 to rotate, at this time, under the centrifugal action of the drying cylinder 301, the wet ammonium sulfate in the drying cylinder 301 separates the leacheate and the wet ammonium sulfate from each other through the hole groove on the drying cylinder 301, and the leacheate can be discharged outwards through the drain pipe 7. After the centrifugal separation operation is completed, an external controller starts the induction coil 8 to heat the interior of the cleaning and drying box 1, and the centrifuged wet product ammonium sulfate can be dried, so that the finished product ammonium sulfate is formed.
What needs to be specifically stated is: the arc-shaped rotating plate 13 and the arc-shaped baffle 303 are provided with a clamping assembly at the end part far away from the rotating shaft center, the clamping assembly comprises a clamping block 15 and an elastic sheet 14, the arc-shaped rotating plate 13 and the arc-shaped baffle 303 are respectively connected with the cleaning drying oven 1 and the side wall opening of the drying cylinder 301 through the clamping assembly in a clamping manner, then the arc-shaped rotating plate 13 and the arc-shaped baffle 303 are sequentially rotated by taking the rotating shaft as the shaft center, at the moment, the clamping block 15 extrudes the elastic sheet 14 under the extrusion of external force, the clamping restriction is canceled, and finished ammonium sulfate inside the drying cylinder 301 can be taken out after the two arc plates are opened. After the material is taken, the arc-shaped rotating plate 13 and the arc-shaped baffle plate 303 are respectively clamped and connected with the cleaning and drying box 1 and the drying cylinder 301 through the clamping assembly, so that the next crystallization can be subjected to spray dehydration and drying operation, and the aim of improving the production efficiency is fulfilled.
Example 2
Step 1: to 100kg of a waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid, 34kg of ammonium bicarbonate was added for reaction while stirring with a stirrer to mix the waste liquid with ammonium bicarbonate sufficiently. After the waste liquid consisting of sulfuric acid, ammonium persulfate and acetic acid reacts with ammonium bicarbonate, when the sulfuric acid and the ammonium persulfate completely react and the solute in the mixed solution is only acetic acid and ammonium sulfate, the pH value of the mixed solution is 2-2.2.
Step 2: and (2) distilling the mixed solution prepared in the step (1) at 100-110 ℃ to obtain 62kg of 41% acetic acid aqueous solution. Cooling to crystallize the mixed solution to obtain 50kg of ammonium sulfate crude product.
Step 3: and (3) leaching the ammonium sulfate crude product generated in the step (2) by using ethanol, and carrying out centrifugal drying on the leached mixed solution to obtain 49kg of wet ammonium sulfate and leaching liquor.
Step 4: and (3) discharging the leaching solution generated in the step (3) outwards, and drying the wet ammonium sulfate to obtain 47kg of finished ammonium sulfate.
Step 5: adding 61kg of water and 17kg of solid sodium hydroxide into the acetic acid aqueous solution obtained by distillation in the step 2, and cooling by circulating water to prepare the sodium acetate aqueous solution with the mass concentration of 25%.
The rest of the implementation methods, equipment mechanisms and operation modes of the embodiment are the same as those of the first embodiment, and are not described in detail.
Example 3
Step 1: to 100kg of a waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid, 34kg of ammonium bicarbonate was added for reaction while stirring with a stirrer to mix the waste liquid with ammonium bicarbonate sufficiently. After the waste liquid consisting of sulfuric acid, ammonium persulfate and acetic acid reacts with ammonium bicarbonate, when the sulfuric acid and the ammonium persulfate completely react and the solute in the mixed solution is only acetic acid and ammonium sulfate, the pH value of the mixed solution is 2-2.2.
Step 2: and (3) distilling the mixed solution prepared in the step (1) at 100-110 ℃ to obtain 65kg of 43% acetic acid aqueous solution. Cooling to crystallize the mixed solution to obtain 55kg of ammonium sulfate crude product.
Step 3: and (3) leaching the ammonium sulfate crude product generated in the step (2) by using ethanol, and carrying out centrifugal drying on the leached mixed solution to obtain 54kg of wet ammonium sulfate and leaching liquor.
Step 4: and (3) discharging the leaching solution generated in the step (3) outwards, and drying the wet ammonium sulfate to obtain 53kg of finished ammonium sulfate.
Step 5: adding 61kg of water and 17kg of solid sodium hydroxide into the acetic acid aqueous solution obtained by distillation in the step 2, and cooling by circulating water to prepare the sodium acetate aqueous solution with the mass concentration of 25%.
The rest of the implementation methods, equipment mechanisms and operation modes of the embodiment are the same as those of the first embodiment, and are not described in detail.
The foregoing description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. A method of treating industrial waste, comprising the steps of:
step 1: adding ammonium bicarbonate into waste liquid composed of sulfuric acid, ammonium persulfate and acetic acid for reaction, stirring by a stirrer to fully mix the waste liquid with the ammonium bicarbonate, and regulating the pH value of the mixed solution to 2-2.2;
step 2: distilling the mixed solution prepared in the step 1 to obtain an acetic acid aqueous solution, and cooling to crystallize the rest mixed solution to obtain an ammonium sulfate crude product;
step 3: eluting the ammonium sulfate crude product generated in the step 2 by ethanol, and carrying out centrifugal drying on the eluted mixed solution to obtain wet ammonium sulfate and eluent;
step 4: discharging the leaching solution generated in the step 3 outwards, and drying wet ammonium sulfate to obtain finished ammonium sulfate;
step 5: adding water and solid sodium hydroxide into the acetic acid aqueous solution obtained by distillation in the step 2, and cooling by circulating water to prepare a sodium acetate aqueous solution with the mass concentration of 25%;
wherein the reactions in step 2, step 3 and step 4 are carried out in an integrated reaction apparatus; the integrated reaction equipment comprises a cleaning and drying box (1) with a distillation tower (4) installed at the top end, an annular pipe (10) is arranged on the outer side of the cleaning and drying box (1), a plurality of shunt pipes (5) penetrating into the cleaning and drying box (1) are formed in circumferential equidistant mode on the outer wall of the annular pipe (10), a spray head used for spraying the cleaning and drying box (1) is fixedly connected to the end portion of each shunt pipe (5), a water pipe (9) is formed on the outer wall of the annular pipe (10), an inductance coil (8) in a threaded mode is installed in the cleaning and drying box (1), a material taking opening (6) penetrating into an inner cavity is formed in the outer wall of the cleaning and drying box (1), and an arc-shaped rotating plate (13) is connected to the material taking opening (6) in a rotating mode through a rotating shaft. A feeding mechanism (2) is arranged in the cleaning drying box (1) and above the annular pipe (10), and the feeding mechanism (2) is used for automatically conveying crystals;
the feeding mechanism (2) comprises: a wall scraping assembly and a lifting assembly; the scraping wall component is arranged in the top end of the cleaning and drying box (1) and is used for automatically scraping off crystals and dumping the crystals; the lifting assembly is arranged below the scraping assembly and is used for shielding sprayed ethanol when the scraping assembly is used for dumping and crystallizing; a centrifugal mechanism (3) is arranged in the cleaning drying box (1) and below the lifting assembly, and the centrifugal mechanism (3) is used for centrifugally dewatering sprayed crystals;
the wall scraping assembly comprises: the cleaning and drying device comprises a driving motor (201) arranged on the outer wall of one end of a cleaning and drying box (1), two overturning plates (203) are symmetrically arranged in the cleaning and drying box (1), the two overturning plates (203) are rotationally connected with the cleaning and drying box (1) through a rotating shaft and a bearing, one overturning plate (203) is fixedly connected with the output end of the driving motor (201) through a connecting shaft, two first gears (204) meshed with each other are arranged on the outer wall of one end, far away from the driving motor (201), of the cleaning and drying box (1), the two first gears (204) are respectively and fixedly connected with the two overturning plates (203) through connecting shafts, positioning plates (2011) are respectively formed at the top ends of the two overturning plates (203), and rotating scraping plates (202) are symmetrically and rotationally connected with the top ends of the positioning plates (2011) through the rotating shaft;
the lifting assembly comprises: the device is characterized in that the device is fixedly connected with a first driving wheel (205) which is far away from one end of the cleaning and drying box (1) through a connecting shaft, a synchronous belt (206) is sleeved on the outer wall of the first driving wheel (205) in a meshed manner, a second driving wheel (207) is sleeved on the inner wall of the bottom end of the synchronous belt (206) in a meshed manner, a second gear (208) which is positioned inside the cleaning and drying box (1) is fixedly connected with one end of the second driving wheel (207) through the connecting shaft, a rack (209) which is connected with the cleaning and drying box (1) in a vertically sliding manner is connected with the outer wall of the second gear (208) in a meshed manner, and a lifting baffle ring (2010) which is connected with the cleaning and drying box (1) in a vertically sliding manner is formed at one end of the rack (209);
the rotating scraper blade (202) rotates along with the rotation of the overturning plate (203) and the locating plate (2011) by taking the rotating shaft as the axis, and simultaneously, the rotating scraper blade (202) can rotate along the outer walls of the overturning plate 203 and the locating plate 2011 under the guidance of the outer walls of the locating plate (2011) by setting the weight of the rotating end of the rotating scraper blade (202) to be larger than one end of the rotating axis, so that crystals on the upper surfaces of the overturning plate (203) and the locating plate (2011) can drop into the drying cylinder (301), and meanwhile, the crystals on the outer walls of the overturning plate (203) and the locating plate (2011) can be scraped through the rotating scraper blade (202).
2. The method for treating industrial waste liquid according to claim 1, wherein in step 1, after the waste liquid consisting of sulfuric acid, ammonium persulfate and acetic acid is reacted with ammonium bicarbonate, when the sulfuric acid and ammonium persulfate are completely reacted and the solute in the mixed solution is only acetic acid and ammonium sulfate, the pH value of the mixed solution is 2 to 2.2.
3. The method for treating industrial waste liquid according to claim 2, wherein the aqueous acetic acid solution obtained by distillation in step 2 has a mass concentration of 40 to 50%.
4. A method of treating industrial waste liquid according to claim 3, wherein the centrifugal mechanism (3) comprises: install inside servo motor (302) in washing drying cabinet (1) bottom, the output fixedly connected with drying cylinder (301) of servo motor (302), drying cylinder (301) are located the below of going up and down baffle ring (2010), take the material mouth has been seted up to the outer wall of drying cylinder (301), the inside of taking the material mouth is connected with arc baffle (303) through the pivot rotation.
5. The method for treating industrial waste liquid according to claim 4, wherein an exhaust pipe (12) is fixedly connected to the top end of the distillation tower (4), a hot and humid air exhaust pipe (11) is fixedly connected to the outer wall of the cleaning and drying box (1), one end of the hot and humid air exhaust pipe (11) inserted into the cleaning and drying box (1) faces the drying cylinder (301), and the other end of the hot and humid air exhaust pipe (11) is connected with an exhaust fan; the exhaust pipe (12) is connected with a collection bin for collecting acetic acid water, a conveying pipe penetrating through the drying box (1) is arranged at the bottom end of the distillation tower (4), and a conveying valve is arranged on the conveying pipe.
6. The method for treating industrial waste liquid according to claim 5, wherein the water pipe (9) is connected with the water tank through a pipeline, a water pump is arranged on the pipeline, a condenser is arranged at the top end of the inner wall of the cleaning and drying box (1), and the induction coil (8) and the condenser are electrically connected with an external controller through wires.
7. The method for treating industrial waste liquid according to claim 6, wherein the cleaning and drying box (1) is provided with a turnover groove for a turnover plate (203) to turn over, a sealing rubber strip is arranged on the peripheral wall of the turnover plate (203), and when the two turnover plates (203) are in a horizontal state, the sealing rubber strip is in sealing contact with the inner wall of the cleaning and drying box (1); a hollow cavity is arranged in the turnover plate (203), and a heat preservation and insulation material is arranged in the hollow cavity; the upper surface of locating plate (2011) is provided with the recess of falling round platform form, the lower surface of rotating scraper blade (202) and the upper surface of locating plate (2011) coincide each other.
8. The method for treating industrial waste liquid according to claim 7, wherein a cavity for heat dissipation is formed inside the cleaning and drying box (1) and outside the servo motor (302), and the outer walls of the drying cylinder (301) and the cleaning and drying box (1) are provided with hole grooves; the outside of servo motor (302) is provided with drain pipe (7) with wash drying cabinet (1) fixed connection, drain pipe (7) run through to the outside of wasing drying cabinet (1) and are used for carrying out the collection box that collects to the leacheate and link to each other.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792796A (en) * | 2005-10-22 | 2006-06-28 | 河北冀衡化学股份有限公司 | Process for recoverying cyanuric acid three wastes |
| CN113475407A (en) * | 2021-06-30 | 2021-10-08 | 金华市农业科学研究院(浙江省农业机械研究院) | Multifunctional pig-raising metabolism cage |
| CN116282655A (en) * | 2023-02-13 | 2023-06-23 | 广东德同环保科技有限公司 | Method for heating, concentrating, crystallizing and cleaning waste sulfuric acid |
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- 2023-07-13 CN CN202310854004.5A patent/CN116573744B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792796A (en) * | 2005-10-22 | 2006-06-28 | 河北冀衡化学股份有限公司 | Process for recoverying cyanuric acid three wastes |
| CN113475407A (en) * | 2021-06-30 | 2021-10-08 | 金华市农业科学研究院(浙江省农业机械研究院) | Multifunctional pig-raising metabolism cage |
| CN116282655A (en) * | 2023-02-13 | 2023-06-23 | 广东德同环保科技有限公司 | Method for heating, concentrating, crystallizing and cleaning waste sulfuric acid |
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