CN114604873A - Process for producing high-dispersion precipitated white carbon black by utilizing recycled waste plastics - Google Patents
Process for producing high-dispersion precipitated white carbon black by utilizing recycled waste plastics Download PDFInfo
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- CN114604873A CN114604873A CN202210300188.6A CN202210300188A CN114604873A CN 114604873 A CN114604873 A CN 114604873A CN 202210300188 A CN202210300188 A CN 202210300188A CN 114604873 A CN114604873 A CN 114604873A
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The invention discloses a process for producing high-dispersion precipitated white carbon black by utilizing recycled waste plastics, which comprises the steps of collecting solid wastes generated in the process of recycling the waste plastics, sieving the solid wastes as raw materials to obtain powder containing silicon dioxide, dissolving the powder by using a sodium hydroxide solution, then introducing the powder into a jacket rotary reactor for heating, adding an additive sodium chloride to remove other metal element impurities in the solution, filtering to obtain refined water glass, reacting the refined water glass and an acidic substance in a reaction kettle at a certain temperature, and finally filtering, washing and drying to obtain a finished product of the high-dispersion precipitated white carbon black. The method utilizes the waste materials generated in the process of recycling the waste plastics to produce the high-dispersion precipitated white carbon black, changes waste materials into valuable materials, realizes the recycling of resources, has simple process flow, saves the consumption of raw materials and energy sources, and has obviously lower production cost than the existing white carbon black production cost.
Description
Technical Field
The invention relates to the technical field of recycling of waste resources, in particular to a process for producing high-dispersion precipitated white carbon black by utilizing recycled waste plastics.
Background
In the existing white carbon black production process, the required silicon dioxide raw material is mined quartz placer or is separated from other materials containing silicon dioxide, the process is complex and tedious, resources are consumed, the cost of the silicon dioxide raw material is high, and finally the production cost of the white carbon black product is high.
In the daily used plastic bag, silicon dioxide is required to be added in the production process to improve the elastic strength, wear resistance, hardness and thermal stability of the plastic bag, and the adding amount of the silicon dioxide is about 3-5% according to different purposes of the plastic bag. The consumption of plastic products in China is remarkable, taking a plastic shopping bag as an object for prohibiting plastic control at a particular place as an example, according to statistics of China's professional committee on recycling of plastic by plastic coordination, about 30 hundred million plastic bags are used every day in China, and as soon as 2019, the annual usage amount of the plastic bags exceeds 400 million tons, and the problem of taking-out and express delivery is aggravated. According to statistics, the annual consumption of Chinese express plastic packages is about 180 ten thousand tons, and the annual consumption of take-out plastic packages is more than 50 ten thousand tons.
The main treatment method of the recycled waste plastic bags in China comprises the following steps: thermal cracking, which is a method for preparing fuel oil and fuel gas by thermally cracking selected waste plastics; energy recovery means to recover the heat generated by burning the waste plastics for other purposes. However, at present, the waste plastic bags are recycled through the two modes, and the generated solid waste is not subjected to subsequent treatment, so that resources are wasted.
Disclosure of Invention
Aiming at the problems, the invention provides a process for producing high-dispersion precipitated white carbon black by utilizing recycled waste plastics, which can directly utilize solid wastes generated in the process of recycling the waste plastics as raw materials to produce the precipitated white carbon black, has simple process flow and low cost, changes waste into valuable and realizes the cyclic utilization of resources.
The technical scheme of the invention is as follows:
the invention provides a process for producing high-dispersion precipitated white carbon black by utilizing recycled waste plastics, which comprises the following steps of: s1, obtaining solid waste raw materials generated in the process of recycling waste plastics, and sieving the solid waste raw materials to obtain powder containing silicon dioxide; s2, mixing, stirring and dissolving the powder material and a sodium hydroxide solution with the mass concentration of 10% -40%; s3, conveying the stirred material to a jacket rotary reactor, heating the material to 60-90 ℃ by steam, adding an additive sodium chloride after a period of time to enable part of precipitated silica colloid to wrap other metal element impurities to be precipitated, wherein the solution in the jacket rotary reactor is crude water glass; s4, conveying the crude water glass to a filtering device for filtering to obtain refined water glass; s5, mixing and stirring the refined water glass and at least one or more of hydrochloric acid, sulfuric acid or carbon dioxide in proportion in a reaction kettle at the temperature of 60-99 ℃ until the pH value of the solution in the reaction kettle is 3-5, and filtering, washing and drying after the reaction is finished to obtain a finished product of the high-dispersion precipitated white carbon black; wherein the mass concentration of the hydrochloric acid is between 10 and 35 percent, and the mass concentration of the sulfuric acid is between 10 and 60 percent.
The working principle of the technical scheme is as follows:
the method comprises the steps of collecting solid wastes generated in the process of recycling waste plastics, sieving the solid wastes serving as raw materials to obtain powder containing silicon dioxide, dissolving the powder with a sodium hydroxide solution, then introducing the solution into a jacket rotary reactor for heating, adding an additive sodium chloride to remove other metal element impurities in the solution, filtering to obtain refined water glass, reacting the refined water glass with an acidic substance in a reaction kettle at a certain temperature, and finally filtering, washing and drying to obtain a finished product of the high-dispersion precipitated white carbon black. The method utilizes the waste materials generated in the process of recycling the waste plastics to produce the high-dispersion precipitated white carbon black, changes waste materials into valuable materials, realizes the recycling of resources, has simple process flow, saves the consumption of raw materials and energy sources, and has obviously lower production cost than the existing white carbon black production cost.
In a further technical solution, step S2 specifically includes: adding water into a batching tank, then adding a sodium hydroxide solution with the mass concentration of 20% -40%, starting a batching tank stirring system, gradually adding the powder and uniformly stirring; wherein the mass of the sodium hydroxide solution is 1-2 times of the mass of the powder.
In a further technical scheme, the mass concentration of the sodium hydroxide solution is 30 +/-2%; the mass of the sodium hydroxide solution is 1.5 +/-0.2 times of the mass of the powder.
In a further technical scheme, in the step S3, the period of time is 40-60 minutes, and the constant temperature state is kept in the period of time.
In a further embodiment, in step S3, the steam is heated to 75 ± 5 ℃ for 50 ± 5 minutes.
In a further technical solution, step S5 specifically includes:
conveying hydrochloric acid to a first metering tank for later use through a first metering pump; conveying the refined water glass to a second metering tank for later use through a second metering pump;
adding a certain amount of water glass into a reaction kettle, introducing steam, heating to a first preset temperature, adding hydrochloric acid in a first metering tank and refined water glass in a second metering tank at a set flow rate within 30-60 minutes, and keeping the first preset temperature for 5-25 minutes; wherein the first preset temperature is 70-90 ℃;
then heating to a second preset temperature, adding hydrochloric acid in the first metering tank and refined water glass in the second metering tank at the same time at a set flow rate, continuously adding the hydrochloric acid until the pH value of the solution is between 3 and 5, and keeping the second preset temperature for more than 20 minutes; wherein the second preset temperature is 2-10 ℃ higher than the first preset temperature;
and filtering and washing the reacted materials, pulping the filter cake, and then sending the pulped material into a spray dryer for drying to obtain a finished product of the high-dispersion precipitated white carbon black.
The hydrochloric acid and the refined water glass are added into the reaction kettle at the same time, so that sufficient reaction can be effectively guaranteed, and meanwhile, the temperature of the reaction kettle is increased for the second time, the solution environment is controlled in an acid environment, so that the refined water glass can be further guaranteed to completely participate in the reaction and precipitate the white carbon black.
In a further technical scheme, the first preset temperature is 80 +/-5 ℃, and the second preset temperature is 5 +/-3 ℃ higher than the first preset temperature; and/or the concentration of the hydrochloric acid is 30 +/-5%.
In a further technical scheme, 45 +/-5 minutes are taken out from the 30-60 minutes; keeping the first preset temperature for 15 +/-5 minutes; and keeping the second preset temperature for more than 30 minutes.
In a further technical scheme, the powder obtained by sieving is 200 meshes or more.
The invention has the beneficial effects that:
1. the method utilizes the waste materials generated in the process of recycling the waste plastics to produce the high-dispersion precipitated white carbon black, changes waste materials into valuable materials, realizes the recycling of resources, has simple process flow, saves the consumption of raw materials and energy sources, and has the production cost obviously lower than the production cost of the existing white carbon black;
2. the hydrochloric acid and the refined water glass are added into the reaction kettle at the same time, so that sufficient reaction can be effectively guaranteed, and meanwhile, the temperature of the reaction kettle is increased for the second time, the solution environment is controlled in an acid environment, so that the refined water glass can be further guaranteed to completely participate in the reaction and precipitate the white carbon black.
Drawings
FIG. 1 is a flow chart of a process for producing highly dispersed precipitated silica from recycled waste plastics according to an embodiment of the present invention.
Detailed Description
The embodiments of the present invention will be further described with reference to the accompanying drawings.
Examples
As shown in FIG. 1, the invention provides a process for producing high-dispersion precipitated silica by using recycled waste plastics, which comprises the following steps:
s1, obtaining solid waste raw materials generated in the process of recycling waste plastics, and sieving to obtain powder containing silicon dioxide. Here, the means for recycling the waste plastics include thermal cracking recycling and direct combustion recycling.
S2, mixing and stirring the powder material and a sodium hydroxide solution with the mass concentration of 10% -40% for dissolution. For example, the sodium hydroxide solution may have a mass concentration of 20%, 30%, or 40%.
S3, conveying the stirred material to a jacket rotary reactor, heating the material to 60-90 ℃ by steam, adding an additive sodium chloride after a period of time to enable part of precipitated silica colloid to wrap other metal element impurities to be precipitated, and obtaining the solution in the jacket rotary reactor as crude water glass. For example, other metal element impurities including iron, magnesium, calcium, etc. can be removed to a level below 100ppm by adding sodium chloride to the sodium silicate material. For example, the steam heating may be carried out at a temperature of 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C.
S4, conveying the crude water glass to a filtering device for filtering to obtain refined water glass. For example, the filtration apparatus may be a filter press.
S5, mixing and stirring the refined water glass and at least one or more of hydrochloric acid, sulfuric acid or carbon dioxide in proportion in a reaction kettle at the temperature of 60-99 ℃ until the pH value of the solution in the reaction kettle is 3-5, and filtering, washing and drying after the reaction is finished to obtain a finished product of the high-dispersion precipitated white carbon black; wherein the mass concentration of the hydrochloric acid is between 10 and 35 percent, and the mass concentration of the sulfuric acid is between 10 and 60 percent. For example, the temperature of the reaction vessel may be 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃. For example, the concentration of the hydrochloric acid may be 15%, 20%, 25%, 30%, and the concentration of the sulfuric acid may be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%. For example, hydrochloric acid or sulfuric acid may be used alone, respectively. In addition, other non-metallic acids of the same type may be used as long as the solution does not precipitate extra precipitates and white carbon black (such as hydrofluoric acid) is not dissolved.
The working principle of the technical scheme is as follows:
the method comprises the steps of collecting solid wastes generated in the process of recycling waste plastics, sieving the solid wastes serving as raw materials to obtain powder containing silicon dioxide, dissolving the powder with a sodium hydroxide solution, then introducing the solution into a jacket rotary reactor for heating, adding an additive sodium chloride to remove other metal element impurities in the solution, filtering to obtain refined water glass, reacting the refined water glass with an acidic substance in a reaction kettle at a certain temperature, and finally filtering, washing and drying to obtain a finished product of the high-dispersion precipitated white carbon black. The method utilizes the waste materials generated in the waste plastic recycling process to produce the high-dispersion precipitated white carbon black, changes waste materials into valuable materials, realizes the recycling of resources, has simple process flow, saves the consumption of raw materials and energy sources, and has the production cost obviously lower than the production cost of the existing white carbon black (for example, the production cost of the white carbon black of the application is lower than more than 10 percent of the production cost of the white carbon black of the prior art by data statistics).
In another embodiment, step S2 specifically includes: adding water into a batching tank, then adding a sodium hydroxide solution with the mass concentration of 20-40%, starting a stirring system of the batching tank, gradually adding the powder and uniformly stirring; wherein the mass of the sodium hydroxide solution is 1-2 times of the mass of the powder.
In further embodiments, the sodium hydroxide solution has a mass concentration of 30 ± 2%; the mass of the sodium hydroxide solution is 1.5 +/-0.2 times of the mass of the powder.
In a further embodiment, in step S3, the period of time is 40-60 minutes during which a constant temperature state is maintained.
In a further embodiment, in step S3, the steam is heated to 75 ± 5 ℃ for a period of 50 ± 5 minutes.
In another embodiment, step S5 specifically includes:
conveying hydrochloric acid to a first metering tank for later use through a first metering pump; conveying the refined water glass to a second metering tank for later use through a second metering pump;
adding a certain amount of water glass into a reaction kettle, introducing steam, heating to a first preset temperature, adding hydrochloric acid in the first metering tank and refined water glass in the second metering tank at the same time within 30-60 minutes at a set flow rate, and keeping the first preset temperature for 5-25 minutes; wherein the first preset temperature is 70-90 ℃;
then heating to a second preset temperature, adding hydrochloric acid in the first metering tank and refined water glass in the second metering tank at the same time at a set flow rate, continuously adding the hydrochloric acid until the pH value of the solution is between 3 and 5, and keeping the second preset temperature for more than 20 minutes; wherein the second preset temperature is 2-10 ℃ higher than the first preset temperature;
and filtering and washing the reacted materials, pulping the filter cake, and then sending the pulped material into a spray dryer for drying to obtain a finished product of the high-dispersion precipitated white carbon black.
Through adding hydrochloric acid and refined sodium silicate into reation kettle simultaneously, can effectively guarantee abundant reaction, through the temperature that promotes reation kettle for the second time and with solution environment control in acid environment simultaneously, can further guarantee that refined sodium silicate has participated in the reaction completely and has appeared and deposit white carbon black.
In further embodiments, the first preset temperature is 80 ± 5 ℃ and the second preset temperature is 5 ± 3 ℃ greater than the first preset temperature; and/or the concentration of the hydrochloric acid is 30 +/-5%.
In further embodiments, 45 ± 5 minutes out of the 30-60 minutes; keeping the first preset temperature for 15 +/-5 minutes; and keeping the second preset temperature for more than 30 minutes.
In another embodiment, the powder obtained by sieving is 200 mesh and above.
The present invention will be specifically described below by way of an example.
1. During the recovery process of preparing combustion oil and fuel gas by thermal cracking of waste plastics, or during the heat recovery process of burning waste plastics, ash powder generated is sieved by a disc stainless steel sieving machine (200-mesh sieving), mechanical impurities in powder are removed, and 100Kg of material is prepared.
2. 400 liters of process water is added into a stainless steel batching tank with the volume of 500L, 148Kg of 30 percent sodium hydroxide solution is added by a metering pump, a stirring system of the batching tank is started, the rotating speed of a stirrer is set at 65 revolutions per minute, 100Kg of sieved powder is added, and the materials are stirred uniformly.
3. The materials stirred uniformly in the proportioning tank are conveyed to the volume of 0.5m by a slurry pump3In the jacket rotary reactor, the rotary reactor rotates at a speed of 17 r/min, 0.3MPa low-pressure steam is used for heating in the jacket, the materials in the rotary reactor are heated to 75 ℃, and the temperature is kept for 50 min.
4. To the jacketed reactor was added 0.1Kg of sodium chloride and the temperature was kept constant at 75 ℃ for 10 minutes. At this time, the reactant obtained in the rotary reactor was a crude water glass liquid having a modulus of 3.
5. Opening the discharge valve of the rotary reactor, and adding the crude water glass liquid of the reaction liquid in the rotary reactor to 1m3A stainless steel liquid storage tank.
6. Conveying the crude water glass liquid in the liquid storage tank to a filter press by using a centrifugal pump for filtering, wherein filter residues are colloid impurities containing iron, calcium, magnesium and the like. The filtrate has modulus of 3, Na2SiO3Refined water glass with the concentration of 20 percent.
7. Respectively conveying 100Kg of 30% finished hydrochloric acid to a hydrochloric acid metering tank by using a hydrochloric acid metering pump for later use; and conveying 500Kg of refined water glass to a water glass metering tank by using a refined water glass metering pump for later use.
8. Adding a certain amount of water and water glass into a reaction kettle, stirring, directly introducing steam, heating to 75 ℃, and simultaneously adding 45Kg of hydrochloric acid in a metering tank and 300Kg of water glass in the metering tank within 45 minutes at a set flow rate. The temperature is kept for 15 minutes, then the temperature is increased to 80 ℃, and 50Kg of hydrochloric acid and 200Kg of water glass in the metering tank are respectively added for 60 minutes at the same time for the second time. After the metered water glass is added, keeping the temperature of the materials in the reaction kettle at 80 ℃, and continuously adding the residual hydrochloric acid in the hydrochloric acid metering tank until the set pH value is 3-5. Keeping the temperature at the temperature for 30 minutes, pumping the mixture into a curing tank by using a conveying pump, filtering the mixture by using a filter press, washing the mixture, pulping a filter cake, drying the mixture in a spray dryer, collecting the dried mixture, and metering and packaging the dried mixture by using an automatic packaging machine to obtain 100Kg of finished high-dispersion precipitated white carbon black.
9. Sampling the product, and carrying out assay analysis according to the high-dispersion precipitated silica standard, wherein the quality indexes of the product and the high-dispersion precipitated silica quality indexes are shown in a table 1:
TABLE 1 comparison of sample quality index with quality index of highly dispersed precipitated silica
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. A process for producing high-dispersion precipitated white carbon black by utilizing recycled waste plastics is characterized by comprising the following steps:
s1, obtaining solid waste raw materials generated in the process of recycling waste plastics, and sieving the solid waste raw materials to obtain powder containing silicon dioxide;
s2, mixing, stirring and dissolving the powder material and a sodium hydroxide solution with the mass concentration of 10% -40%;
s3, conveying the stirred material to a jacket rotary reactor, heating the material to 60-90 ℃ by steam, adding an additive sodium chloride after a period of time to enable part of precipitated silica colloid to wrap other metal element impurities to be precipitated, wherein the solution in the jacket rotary reactor is crude water glass;
s4, conveying the crude water glass to a filtering device for filtering to obtain refined water glass;
s5, mixing and stirring the refined water glass and at least one or more of hydrochloric acid, sulfuric acid or carbon dioxide in proportion in a reaction kettle at the temperature of 60-99 ℃ until the pH value of the solution in the reaction kettle is 3-5, and filtering, washing and drying after the reaction is finished to obtain a finished product of the high-dispersion precipitated white carbon black; wherein the mass concentration of the hydrochloric acid is between 10 and 35 percent, and the mass concentration of the sulfuric acid is between 10 and 60 percent.
2. The process for producing high-dispersion precipitated silica by using recycled waste plastics according to claim 1, wherein the step S2 specifically comprises: adding water into a batching tank, then adding a sodium hydroxide solution with the mass concentration of 20-40%, starting a stirring system of the batching tank, gradually adding the powder and uniformly stirring; wherein the mass of the sodium hydroxide solution is 1-2 times of the mass of the powder.
3. The process for producing high-dispersion precipitated silica by using recycled waste plastics as claimed in claim 2, wherein the mass concentration of the sodium hydroxide solution is 30 ± 2%; the mass of the sodium hydroxide solution is 1.5 +/-0.2 times of the mass of the powder.
4. The process for producing highly dispersed precipitated silica according to claim 1, wherein the period of time is 40 to 60 minutes while maintaining a constant temperature state in step S3.
5. The process for producing highly dispersed precipitated silica according to claim 4, wherein the steam is heated to 75 ± 5 ℃ for 50 ± 5 minutes in step S3.
6. The process for producing high-dispersion precipitated silica by using recycled waste plastics according to claim 1, wherein the step S5 specifically comprises:
conveying hydrochloric acid to a first metering tank for later use through a first metering pump; conveying the refined water glass to a second metering tank for later use through a second metering pump;
adding a certain amount of water glass into a reaction kettle, introducing steam, heating to a first preset temperature, adding hydrochloric acid in a first metering tank and refined water glass in a second metering tank at a set flow rate within 30-60 minutes, and keeping the first preset temperature for 5-25 minutes; wherein the first preset temperature is 70-90 ℃;
then heating to a second preset temperature, adding hydrochloric acid in the first metering tank and refined water glass in the second metering tank at the same time at a set flow rate, continuously adding the hydrochloric acid until the pH value of the solution is between 3 and 5, and keeping the second preset temperature for more than 20 minutes; wherein the second preset temperature is 2-10 ℃ higher than the first preset temperature;
and filtering and washing the reacted materials, pulping the filter cake, and then sending the pulped material into a spray dryer for drying to obtain a finished product of the high-dispersion precipitated white carbon black.
7. The process for producing high-dispersion precipitated silica by using recycled waste plastics as claimed in claim 6, wherein the first preset temperature is 80 ± 5 ℃, and the second preset temperature is greater than the first preset temperature by 5 ± 3 ℃; and/or the concentration of the hydrochloric acid is 30 +/-5%.
8. The process for producing high-dispersion precipitated silica by using recycled waste plastics according to claim 7, wherein 45 ± 5 minutes are taken out from 30-60 minutes; keeping the first preset temperature for 15 +/-5 minutes; and keeping the second preset temperature for more than 30 minutes.
9. The process for producing high-dispersion precipitated silica by using recycled waste plastics according to claim 1, wherein the powder obtained by sieving is 200 meshes or more.
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| US20070280871A1 (en) * | 2004-02-11 | 2007-12-06 | Kandy S.A. | Process For Recovery Of The Silica Present In The Separators Between The Elements Of Lead-Acid Batteries |
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| CN108017066A (en) * | 2017-12-27 | 2018-05-11 | 昌吉吉盛新型建材有限公司 | Utilize the high-purity white carbon and its production method of the production of industrial silicon by-product SILICA FUME |
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2022
- 2022-03-25 CN CN202210300188.6A patent/CN114604873A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070280871A1 (en) * | 2004-02-11 | 2007-12-06 | Kandy S.A. | Process For Recovery Of The Silica Present In The Separators Between The Elements Of Lead-Acid Batteries |
| JP2009227980A (en) * | 2008-02-26 | 2009-10-08 | Panasonic Electric Works Co Ltd | Method for decomposition and recovery of plastic |
| CN101423223A (en) * | 2008-11-12 | 2009-05-06 | 山西天一纳米材料科技有限公司 | Impurity removal and purification method for waterglass |
| CN101983919A (en) * | 2010-11-15 | 2011-03-09 | 桂劲宁 | Method for producing white carbon black by polycrystalline silicon cut waste alkali-wash waste water |
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