CN113666388B - Treatment method of dye wastewater - Google Patents

Treatment method of dye wastewater Download PDF

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CN113666388B
CN113666388B CN202110983798.6A CN202110983798A CN113666388B CN 113666388 B CN113666388 B CN 113666388B CN 202110983798 A CN202110983798 A CN 202110983798A CN 113666388 B CN113666388 B CN 113666388B
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solid product
solid
treatment method
treatment
ammonium
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CN113666388A (en
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刘仲明
丁兴成
沈振雄
王汝�
李家琪
陈清
章妙
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Zhejiang Runtu Institute Co ltd
Zhejiang Runtu Co Ltd
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Zhejiang Runtu Institute Co ltd
Zhejiang Runtu Co Ltd
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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
    • C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/16—Halides of ammonium
    • C01C1/164—Ammonium chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • 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
    • 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
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention provides a method for treating dye wastewater. Wherein, the dye wastewater contains sulfuric acid, and the treatment method comprises the following steps: step 1: neutralizing the dye wastewater by using calcium carbonate, and separating to obtain a first solid product and a first clear liquid; step 2: and treating the first solid product by using ammonium bicarbonate, and performing solid-liquid separation to obtain a second solid product containing calcium carbonate and a second clear liquid. The treatment method of dye wastewater of the invention can have excellent effects: 1) The problem that biochemical bacteria cannot tolerate due to overhigh salt content and overhigh ammonia nitrogen in the wastewater during biochemistry is solved; 2) Toxic and harmful organic matters in the wastewater are treated by biochemical treatment and organic solid waste incineration, and the treatment method is simple and thorough; 3) The obtained ammonium sulfate and ammonium chloride have little organic residue and high quality; 4) Except the solid waste of organic matters, no other dangerous waste is generated.

Description

Treatment method of dye wastewater
Technical Field
The invention relates to the field of water pollution control and wastewater treatment, in particular to a method for treating dye wastewater containing low-concentration sulfuric acid.
Background
The dye production process generates a lot of sulfuric acid-containing mother liquor water and contains a lot of organic matters. For the treatment of such acid-containing wastewater, wastewater with higher sulfuric acid concentration can be treated by a method of recovering ammonium sulfate product by evaporation after neutralization with aqueous ammonia, and the method has the disadvantages that the treatment of organic matters in waste acid is difficult, and the quality of the obtained ammonium sulfate salt is poor.
In patent document CN108569812A, activated carbon is used to adsorb and remove organic matters in wastewater containing low-concentration sulfuric acid, then calcium carbonate is used to neutralize sulfuric acid in the wastewater, the generated calcium sulfate is pulped, and is mixed with ammonium carbonate to generate a double decomposition reaction to generate ammonium sulfate and calcium carbonate, so as to realize cyclic utilization of calcium carbonate. The disadvantages of this process are (1) the production of large quantities of spent activated carbon; (2) A large amount of ammonium sulfate exists in calcium carbonate, so that the ammonia nitrogen in the neutralized wastewater exceeds the standard; (3) Part of organic matters and impurities which do not participate in the reaction are enriched in the calcium carbonate circulation, and finally, the calcium carbonate cannot be recycled.
Disclosure of Invention
Problems to be solved by the invention
In view of the above technical problems in the prior art, the present invention provides a method for treating dye wastewater, which reduces the difficulty of treating wastewater containing low-concentration sulfuric acid.
Means for solving the problems
The invention provides a treatment method of dye wastewater, wherein the dye wastewater contains sulfuric acid, and the treatment method comprises the following steps:
step 1: neutralizing the dye wastewater by using calcium carbonate, and separating to obtain a first solid product and a first clear liquid;
step 2: and treating the first solid product by using ammonium bicarbonate, and performing solid-liquid separation to obtain a second solid product containing calcium carbonate and a second clear solution.
According to the treatment method of the present invention, in the step 1, the solid-liquid separation is performed until the pH of the dye wastewater is 4.0 to 5.0 after the neutralization treatment.
The treatment method according to the invention, wherein, before treating the first solid product with ammonium bicarbonate, the step 2 further comprises pulping the first solid product to obtain solid slurry, and treating the solid slurry with ammonium bicarbonate;
preferably, before the first solid product is treated by ammonium bicarbonate, and/or during the treatment of the first solid product by ammonium bicarbonate, ammonia water is used for controlling the pH value of the reaction system to be 6-8.
The treatment method comprises the following steps of (1) enabling the mass concentration of the solid slurry to be 10-44%, preferably 15-25%; and/or
The mass ratio of the first solid product to the ammonium bicarbonate is 2-6.
The treatment method provided by the invention is characterized in that the COD value of the second clear liquid in the step 2 is less than 1000mg/L; preferably, the step 2 further comprises evaporating and crystallizing the second clear solution to obtain ammonium sulfate.
The processing method according to the present invention, wherein the processing method further comprises:
when the organic content in the second solid product is lower than 8wt%, the second solid product containing calcium carbonate is used for carrying out neutralization treatment on the next batch of dye wastewater.
The processing method according to the present invention, wherein the processing method further comprises: and when the content of the organic matters in the second solid product is more than 8wt%, neutralizing the second solid product, and separating to obtain an organic solid product and a solution containing calcium ions.
The treatment method provided by the invention is characterized in that the pH value of the solution containing calcium ions is 6-8, and the COD is less than 1000mg/L; and/or, the organic matter content in the organic solid product is more than 80wt%.
The treatment method according to the present invention, wherein the solution containing calcium ions is treated with ammonium bicarbonate to obtain a solution containing ammonium ions and a third solid product, which can be used for the neutralization treatment in step 1.
According to the treatment method, the solution containing the ammonium ions is subjected to evaporative crystallization to obtain the ammonium salt.
ADVANTAGEOUS EFFECTS OF INVENTION
The method for treating the dye wastewater has one of the following excellent effects:
1) The problem that biochemical bacteria cannot tolerate due to overhigh salt content and overhigh ammonia nitrogen in the wastewater during biochemistry is solved;
2) Toxic and harmful organic matters in the wastewater are treated by biochemical treatment and organic solid waste incineration, and the treatment method is simple and thorough;
3) The obtained ammonium sulfate and ammonium chloride have little organic residue and high quality;
4) No other dangerous waste is generated except the organic solid waste;
5) The dye wastewater treatment method has low requirements on wastewater, corrosion resistance and automation, so the method has low operation cost and is suitable for industrial treatment.
Drawings
Fig. 1 shows a process flow diagram of dye wastewater containing low-concentration sulfuric acid according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end points of numerical values a and B.
In the present specification, "plural" in "plural", and the like means a numerical value of 2 or more unless otherwise specified.
In this specification, the terms "substantially", "substantially" or "substantially" mean an error of less than 5%, or less than 3% or less than 1% as compared to the relevant perfect or theoretical standard.
In the present specification, "%" represents mass% unless otherwise specified.
In the present specification, the term "may" includes both the case where a certain process is performed and the case where no process is performed.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
The 'normal temperature' and 'room temperature' of the invention can be 10-40 ℃ generally.
The invention firstly provides a treatment method of dye wastewater, wherein the dye wastewater contains sulfuric acid, and the treatment method comprises the following steps:
step 1: neutralizing the dye wastewater by using calcium carbonate, and performing solid-liquid separation to obtain a first solid product and a first clear solution;
and 2, step: and treating the first solid product by using ammonium bicarbonate, and performing solid-liquid separation to obtain a second solid product containing calcium carbonate and a second clear liquid.
Specifically, in the present invention, the mass content of sulfuric acid in the dye wastewater may be 1 to 8%. The treatment method of the dye wastewater reduces the treatment difficulty of the wastewater containing low-concentration sulfuric acid.
In some specific embodiments, in the step 1, the neutralization treatment is performed until the pH value of the dye wastewater is 4.0 to 5.0, and then solid-liquid separation is performed. That is, in step 1, the end point of the neutralization reaction is determined when the pH value of the dye wastewater is 4.0-5.0. Specifically, when the pH values measured twice at intervals of 15 minutes are both 4.0 to 5.0, it can be said that the end point of the neutralization reaction is reached. Preferably, the calcium carbonate used in the present invention is a technical grade calcium carbonate having a calcium carbonate content of 95% or more.
Further, the water content in the first solid product of the invention may be below 50%, for example: 48% or less, 45% or less, 42% or less, 40% or less, 38% or less, 35% or less, 33% or less, 30% or less, and the like. The lower water content in the first solid product facilitates the performance of step 2 and in particular the reduction of the COD value of the second clear liquid of step 2.
In the invention, the first clear liquid can be separated by using calcium carbonate to treat the dye wastewater, and particularly, the COD value of the first clear liquid is less than 3000mg/L, the salt content is less than 0.8 percent, and the first clear liquid can be directly subjected to biochemical treatment because the COD value is small and the salt content is also low enough. The biochemical treatment method is not particularly limited, and may be a biochemical treatment method commonly used in the art, that is, a biochemical treatment method is used to biochemically treat the first clear liquid. Specifically, the biochemical method may be an activated sludge method and/or a biofilm method.
In some embodiments, step 2 further comprises slurrying the first solid product to obtain a solid slurry prior to treating the first solid product with ammonium bicarbonate, and treating the solid slurry with ammonium bicarbonate.
Preferably, before the first solid product is treated by ammonium bicarbonate, and/or during the treatment of the first solid product by ammonium bicarbonate, ammonia water is used for controlling the pH value of the reaction system to be 6-8. Namely, the pH value of the solid slurry can be controlled to be 6-8 by using an alkaline agent, and then the solid slurry is treated by using ammonium bicarbonate, and the pH value of the solid slurry is controlled to be 6-8 all the time in the treatment process. The alkaline agent is not particularly limited in the present invention, and may be any of those commonly used in the art, and ammonia is preferably used as the alkaline agent for adjusting the pH in consideration of the COD value after the treatment, the salt content, and the like.
Specifically, if the water content in the first solid product is low, some water may be appropriately added to facilitate beating, and the amount of water added is not particularly limited, and may be determined according to the water content in the first solid product. In consideration of the subsequent further treatment, the content of water added may be such that the final solid slurry has a mass concentration of 10% to 44%, preferably 15% to 35%, for example: 12%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, etc.
Further, in the present invention, the mass ratio of the first solid product to the ammonium bicarbonate can be 2-6: 2.5. When the mass ratio of the first solid product to the ammonium bicarbonate is 2-6, the reaction can be completed as completely as possible, and the subsequent treatment is facilitated to be carried out.
In addition, in some specific embodiments, the second solid product obtained may be recycled according to the content of organic matters or the content of calcium carbonate therein.
Specifically, the processing method may further include: and when the organic content in the second solid product is lower than 8wt%, performing neutralization treatment on the next batch of dye wastewater by using the second solid product containing calcium carbonate. This is because, if the organic matter content is too high, the dye wastewater is polluted again, and the treatment difficulty is increased, so that the organic matter content of less than 8wt% can be used for the neutralization treatment of the next batch of the dye wastewater.
Further, the processing method may further include: when the organic content in the second solid product is more than 8wt%, the second solid product can be neutralized and then separated to obtain an organic solid product and a solution containing calcium ions.
Specifically, the mode of neutralization treatment is not particularly limited in the present invention, and the second solid product can be dissolved with a commonly used acid agent, and it is preferable to use hydrochloric acid as the acid agent in view of the COD value after dissolution and the salts required in the art. The concentration of hydrochloric acid is not particularly limited in the present invention, and may be suitably selected, and specifically, the concentration of hydrochloric acid may be 10 to 35%, for example: 15%, 20%, 25%, 30%, etc.
In addition, in the organic solid product obtained by the invention, the content of the organic matters is more than 80wt%, and the content of the ash content is less than 20wt%. The organic matter can be directly incinerated, the treatment method is simple and thorough, and no more residues are left.
Furthermore, the pH value of the solution containing calcium ions obtained by the invention is 6-8, and the COD is less than 1000mg/L. The calcium ion-containing solution may be further treated to obtain other desired substances. In particular, the solution containing calcium ions can be treated with ammonium bicarbonate to obtain a solution containing ammonium ions and a third solid product, the third solid product has a very high calcium carbonate content and can be used for the neutralization treatment in step 1 of the present invention.
Specifically, ammonium bicarbonate is added into the solution containing calcium ions, ammonia water is used for controlling the pH value in the whole reaction process to be 6-8, and the calcium carbonate is prepared after solid-liquid separation and washing. Wherein the washing water may be combined with the separated solution containing ammonium ions for further treatment. Specifically, the solution containing ammonium ions is subjected to evaporative crystallization to obtain ammonium salt. The purity of the ammonium salt obtained by the invention can reach more than 90%, preferably more than 95%, and more preferably more than 98%.
The solid-liquid separation method is not particularly limited in the present invention, and the solid-liquid separation can be performed by filtration (for example, filter pressing) or centrifugation.
The method greatly reduces the treatment difficulty of the wastewater containing low-concentration sulfuric acid: the beneficial effects can be embodied in the following aspects: 1) The problem that biochemical bacteria cannot tolerate due to overhigh salt content and overhigh ammonia nitrogen in the wastewater during biochemistry is avoided; 2) Toxic and harmful organic matters in the wastewater are treated by biochemical treatment and organic solid waste incineration, and the treatment method is simple and thorough; 3) The obtained ammonium sulfate and ammonium chloride has little organic residue and high quality. 4) Except the solid waste of organic matters, no other dangerous waste is generated.
Furthermore, the method has low requirements on wastewater, corrosion resistance on equipment and automation, so that the method has low operation cost and is suitable for industrial treatment.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
Example 1
The sulfur acid-containing wastewater produced in the production process of a certain dye from a certain large dye company in Zhejiang contains about 2.6wt% of sulfur acid and 4800mg/L of COD. The method comprises the following steps:
step 1, neutralizing the sulfuric acid-containing wastewater by using light calcium carbonate (with the content of 97%) in batches (neutralizing by using a calcium carbonate filter cake obtained by a reaction subsequently, and supplementing new calcium carbonate) to obtain a suspension, and controlling the pH of a neutralization end point to be 4.0-5.0.
And 2, carrying out filter pressing separation on the turbid liquid obtained in the step 1 to obtain a first solid product (calcium sulfate filter cake) and a clear liquid with low salt content. Wherein the water content of the calcium sulfate filter cake is 45 percent; the COD of the clear liquid with low salt content is 1630mg/L, the salt content is less than 0.5 percent, and the clear liquid can be used for biochemical treatment.
And 3, pulping the first solid product (calcium sulfate filter cake (with water content of 45 percent)) and water according to a ratio of 1.2, controlling the pH value in the reaction process to be 6-8 by using ammonia water at the temperature of 30 ℃, slowly adding ammonium bicarbonate, and enabling the pH value in the reaction process to be 6-8. Wherein the mass ratio of the first solid product (calcium sulfate filter cake) to the ammonium bicarbonate is 3.2. And after reaction, performing filter pressing and cleaning, and combining washing water with the filtrate to obtain a second clear liquid (ammonium sulfate solution) and a second solid product (calcium carbonate filter cake), wherein the COD of the second clear liquid (ammonium sulfate solution) is 570mg/L.
And 4, evaporating, centrifuging and drying the ammonium sulfate solution obtained in the step 3 to obtain ammonium sulfate. Wherein the purity of the ammonium sulfate solid is about 99 percent.
And 5, recycling the second solid product (calcium carbonate filter cake) obtained in the step 3 back to the step 1, and repeating the steps 1-4.
And 6, neutralizing the second solid product (calcium carbonate filter cake with the organic matter content of 9.1 wt%) which is repeatedly used with hydrochloric acid, controlling the pH value at the end point of the reaction to be 6-8, and controlling the concentration of the used hydrochloric acid to be 30%. Filter pressing and separating to obtain an organic solid product (organic filter cake) and a calcium chloride solution. After the organic solid product (organic filter cake) is dried, the ash content of the dried organic solid product is 12.4 percent by using a muffle furnace, and the COD of the calcium chloride solution is 380mg/L.
And 7, adding ammonium bicarbonate into the calcium chloride solution, controlling the pH value to be 6-8 in the process by using ammonia water, performing filter pressing and washing, and combining washing water with the filtrate to obtain a third solid product (a calcium carbonate filter cake) and an ammonium chloride solution. The mass concentration of the ammonium chloride solution was 20%, and COD =257mg/L. And detecting after drying the third solid product (calcium carbonate filter cake) to obtain a calcium carbonate content of more than 99%.
And 8, evaporating, centrifuging and drying the ammonium chloride solution obtained in the step 7 to obtain ammonium chloride. Wherein the purity of the ammonium chloride solid is about 99 percent.
And 9, continuously applying the calcium carbonate filter cake obtained in the step 7 to wastewater treatment.
Example 2
The sulfur acid-containing wastewater produced in the production process of certain dye from certain dye company in Zhejiang contains about 7.1% of sulfur acid and 14000mg/L of COD. The method comprises the following steps:
step 1, neutralizing the sulfuric acid-containing wastewater by using light calcium carbonate (the content is 97%) in batches (neutralizing by using a calcium carbonate filter cake obtained by reaction and supplementing new calcium carbonate to obtain a suspension, and controlling the pH of a neutralization end point to be 4.0-5.0.
And 2, carrying out filter pressing separation on the turbid liquid obtained in the step 1 to obtain a first solid product (calcium sulfate filter cake) and a clear liquid with low salt content. Wherein the first solid product (calcium sulfate filter cake) contains 50% water; the COD of the clear liquid with low salt content is 3150mg/L, the salt content is less than 0.5 percent, and the clear liquid can be used for biochemical treatment.
And 3, pulping the first solid product (calcium sulfate filter cake (containing 50% of water) and water according to a ratio of 1.
And 4, evaporating, centrifuging and drying the second clear liquid (ammonium sulfate solution) obtained in the step 3 to obtain ammonium sulfate. Wherein the purity of the ammonium sulfate solid is about 99 percent.
And 5, recycling the second solid product (calcium carbonate filter cake) obtained in the step 3 back to the step 1, and repeating the steps 1-4.
And 6, neutralizing the second solid product (calcium carbonate filter cake, the content of organic matters is about 8.3 wt%) which is repeatedly used with hydrochloric acid, controlling the pH value at the end point of the reaction to be 6-8, and controlling the concentration of the used hydrochloric acid to be 30%. Filter pressing and separating to obtain an organic solid product (organic filter cake) and a calcium chloride solution. After the organic solid product (organic filter cake) is dried, the ash content of the dried organic solid product is 15.5 percent by using a muffle furnace, and the COD of the calcium chloride solution is 650mg/L.
And 7, adding ammonium bicarbonate into the calcium chloride solution, controlling the pH value to be 6-8 in the process by using ammonia water, performing filter pressing and washing, and combining washing water with the filtrate to obtain a third solid product (a calcium carbonate filter cake) and an ammonium chloride solution. The mass concentration of the ammonium chloride solution was 21%, and COD =410mg/L. And detecting after drying the third solid product (calcium carbonate filter cake), wherein the content of calcium carbonate is more than 99%.
And 8, evaporating, centrifuging and drying the ammonium chloride solution obtained in the step 7 to obtain ammonium chloride. Wherein the purity of the ammonium chloride solid is about 99 percent.
And 9, continuously applying the calcium carbonate filter cake obtained in the step 7 to wastewater treatment.
Example 3
The sulfur acid-containing wastewater produced in the dye production process of a dye company in Zhejiang approximately contains 4.8% of sulfur acid and 8500mg/L of COD. The method comprises the following steps:
step 1, neutralizing the sulfuric acid-containing wastewater by using light calcium carbonate (the content is 97%) in batches (neutralizing by using a calcium carbonate filter cake obtained by reaction and supplementing new calcium carbonate to obtain a suspension, and controlling the pH of a neutralization end point to be 4.0-5.0.
And 2, performing filter pressing separation on the suspension obtained in the step 1 to obtain a first solid product (calcium sulfate filter cake) and a clear liquid with low salt content. Wherein the first solid product (calcium sulfate filter cake) contains 30% water; the COD of the clear liquid with low salt content is 2650mg/L, the salt content is less than 0.5 percent, and the clear liquid can be used for biochemical treatment.
And 3, pulping the first solid product (calcium sulfate filter cake (containing 30% of water) and water according to the proportion of 1 to 2, controlling the pH value in the reaction process to be 6-8 by using ammonia water under the condition of 30 ℃, slowly adding ammonium bicarbonate, and controlling the pH value in the reaction process to be 6-8 by using the ammonia water, wherein the mass ratio of the first solid product (the calcium sulfate filter cake (containing 30% of water) to the ammonium bicarbonate is 2.5, performing pressure filtration and cleaning after reaction, and combining washing water and the filtrate to obtain a second clear liquid (ammonium sulfate solution) and a second solid product (calcium carbonate filter cake), wherein the COD of the second clear liquid (the ammonium sulfate solution) is 460mg/L.
And 4, evaporating, centrifuging and drying the second clear liquid (ammonium sulfate solution) obtained in the step 3 to obtain ammonium sulfate. Wherein the purity of the ammonium sulfate solid is about 99 percent.
And 5, recycling the second solid product (calcium carbonate filter cake) obtained in the step 3 back to the step 1, and repeating the steps 1-4.
And 6, neutralizing the second solid product (calcium carbonate filter cake with the organic matter content of 8.7 wt%) which is repeatedly used with hydrochloric acid, controlling the pH value at the end point of the reaction to be about 7, and controlling the concentration of the used hydrochloric acid to be 30%. Filter pressing and separating to obtain an organic solid product (organic filter cake) and a calcium chloride solution. After the organic solid product (organic filter cake) is dried, the ash content of the dried organic solid product is 13.1 percent by using a muffle furnace, and the COD of the calcium chloride solution is 460mg/L.
And 7, adding ammonium bicarbonate into the calcium chloride solution, controlling the pH value to 6-8 by using ammonia water, performing filter pressing and washing, and combining washing water with the filtrate to obtain a third solid product (calcium carbonate filter cake) and an ammonium chloride solution. The mass concentration of the ammonium chloride solution was 20%, and COD =330mg/L. And detecting after drying the third solid product (calcium carbonate filter cake), wherein the content of calcium carbonate is more than 99%.
And 8, evaporating, centrifuging and drying the ammonium chloride solution obtained in the step 7 to obtain ammonium chloride. Wherein the purity of the ammonium chloride solid is about 99 percent.
And 9, continuously applying the calcium carbonate filter cake obtained in the step 7 to wastewater treatment.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or technical improvements to the market, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims (10)

1. A treatment method of dye wastewater is characterized in that the dye wastewater contains sulfuric acid, and the treatment method comprises the following steps:
step 1: neutralizing the dye wastewater by using calcium carbonate, and separating to obtain a first solid product and a first clear liquid;
step 2: treating the first solid product by using ammonium bicarbonate, and performing solid-liquid separation to obtain a second solid product containing calcium carbonate and a second clear liquid;
when the organic content in the second solid product is lower than 8wt%, utilizing the second solid product containing calcium carbonate to perform neutralization treatment on the next batch of dye wastewater;
when the content of the organic matters in the second solid product is more than 8wt%, neutralizing the second solid product, and separating to obtain an organic solid product and a solution containing calcium ions;
treating the calcium ion-containing solution with ammonium bicarbonate to obtain an ammonium ion-containing solution and a third solid product, which can be used for the neutralization treatment of step 1.
2. The treatment method according to claim 1, wherein in the step 1, the neutralization treatment is performed until the pH of the dye wastewater is 4.0 to 5.0, and then solid-liquid separation is performed.
3. The process of claim 1 or 2, wherein step 2 further comprises slurrying the first solid product to obtain a solid slurry prior to treating the first solid product with ammonium bicarbonate, and treating the solid slurry with ammonium bicarbonate.
4. The treatment method according to claim 3, wherein the pH of the reaction system is controlled to 6 to 8 by using ammonia water before the treatment of the first solid product with ammonium bicarbonate and/or during the treatment of the first solid product with ammonium bicarbonate.
5. The treatment method according to claim 3, wherein the mass concentration of the solid slurry is 10-44%; and/or
The mass ratio of the first solid product to the ammonium bicarbonate is 2-6.
6. The treatment method according to claim 5, wherein the mass concentration of the solid slurry is 15 to 25%.
7. The process according to claim 1 or 2, characterized in that the COD value of the second clear liquid of step 2 is less than 1000mg/L.
8. The process of claim 7, wherein step 2 further comprises subjecting the second clear solution to evaporative crystallization to obtain ammonium sulfate.
9. The treatment method according to claim 1 or 2, wherein the pH value of the calcium ion-containing solution is 6 to 8, cod is less than 1000mg/L; and/or, the organic matter content in the organic solid product is more than 80wt%.
10. The process according to claim 1 or 2, characterized in that the solution containing ammonium ions is subjected to evaporative crystallization to obtain ammonium salts.
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