CN108726537B - Method for recycling ammonium chloride in APT production process - Google Patents
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Abstract
The invention relates to a method for recycling ammonium chloride in the APT production process, which comprises the steps of ammonia activation, stripping, hydrochloric acid spraying and the like, wherein ammonia nitrogen wastewater is adsorbed and pre-activated by pretreated activated carbon before ammonia activation, three-stage stripping is adopted, and a small amount of nitrogen is introduced in the process, so that the concentration of a used sodium hydroxide solution can be reduced, ammonium chloride with higher concentration can be obtained, the requirement of recycling and preparing a desorption solution is met, and the concentration of NH3-N in the deaminated wastewater and the ammonia content of discharged waste gas meet the integrated wastewater discharge standard (GB 3-1996) and the malodorous pollutant discharge standard (GB 14554-93).
Description
Technical Field
The invention relates to a method for recycling ammonium chloride, in particular to a method for recycling ammonium chloride in an APT production process.
Background
Producing Ammonium Paratungstate (APT) by a tungsten smelting ion exchange method, converting a tungsten-containing raw material into a sodium tungstate solution by a pressure alkaline leaching method, adjusting proper alkalinity and tungsten degree, performing ion exchange column exchange, performing tungsten absorption and impurity removal by ion exchange resin, performing desorption by a desorbent (ammonia-ammonium chloride solution), converting tungsten into an ammonium tungstate solution, removing impurities from a desorption solution to obtain a product solution, and performing concentration crystallization, filtration and drying on the product solution to obtain an APT product.
Therefore, the ammonia nitrogen wastewater generated in the smelting process is mainly generated in the ion exchange and APT crystallization processes in the APT production process if NH is not adopted4By taking Cl recovery measures, a large amount of NH can be generated in the production process3The ammonium chloride enters waste gas and waste water, and meanwhile, a certain amount of ammonium chloride solution is needed to prepare the desorbent in the ion exchange process, so that the ammonium chloride is obtained from the ammonia nitrogen waste water generated in the APT production process through certain recovery treatment to prepare the desorbent, and the recycling cycle of the ammonium chloride is formed.
In the existing ammonium chloride recovery, ammonia nitrogen wastewater is mainly subjected to ammonia activation with alkali, the alkali consumption is large, and the concentration of the obtained ammonium chloride is not high, so that the requirement for preparing a desorbent cannot be met.
Disclosure of Invention
The invention aims to provide a method for recycling ammonium chloride in an APT production process, which is characterized in that adsorption and pre-activation treatment are carried out before ammonia activation of ammonia nitrogen wastewater, so that the alkali consumption is reduced, and the concentration of the obtained ammonium chloride is improved by adopting a staged stripping process.
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) adsorbing and pre-activating ammonia nitrogen wastewater by using activated carbon in a clarification tank, and filtering;
(2) pumping the filtered wastewater into a stirring tank, adding a sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
(3) introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding a sodium hydroxide solution to adjust the pH value to 11, and stripping;
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main flow to prepare desorption liquid.
In the step (1), the activated carbon is pretreated, and the specific pretreatment method comprises the following steps: mixing activated carbon with 80-120g/L sodium hydroxide solution, treating at 50-60 deg.C for 40-50 min, and filtering.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 80-120g/L is 1g:2-8 ml.
In the step (1), the feed-liquid ratio of the ammonia nitrogen wastewater to the activated carbon is 1L:0.4-0.6 g.
In the step (2), the concentration of the sodium hydroxide solution is 80-120 g/L.
In the step (2), the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100: 8-12.
In the step (3), the stripping is divided into three stages, wherein air is introduced into the first stage at the temperature of 40-50 ℃ for 20-40 minutes; in the second stage, air and nitrogen are introduced at the temperature of 70-80 ℃ for 20-40 minutes; in the third stage, air is introduced at 55-65 deg.C for 20-40 min.
Wherein, the air flow introduced in the first and the third stages is as follows: 600-; the air flow introduced in the second stage is as follows: 500-650sccm, nitrogen flow rate: 100-.
In the step (3), the sodium hydroxide solution used for adjusting the pH value is the sodium hydroxide filtrate obtained after the pretreatment of the activated carbon in the step (1).
In the step (4), the concentration of the hydrochloric acid is 200-280 g/L.
The ammonia nitrogen wastewater is a mixed solution of column washing water after desorption of the exchange column, kettle residual liquid of crystallized steam after rectification tower and first-stage liquid and fourth-stage liquid after ion exchange, and the ammonia nitrogen concentration is 30-40 g/L.
When the first-stage solution after ion exchange is desorption, the presence of W is detected and WO is detected3The% concentration is less than 80g/L and is received as a first stage liquid when WO3When the% concentration is lower than the requirement, the solution is received as four sections of solution after ion exchange.
The invention has the beneficial effects that:
1. before ammonia activation is carried out on ammonia nitrogen wastewater, pre-activation is carried out on activated carbon pretreated by alkali, the concentration of a used sodium hydroxide solution can be reduced in the subsequent activation process, the concentration can be reduced to 80-120g/L from 150g/L in the prior art, the using amount of sodium hydroxide is reduced, the activated carbon can adsorb impurities and macromolecular particles in the ammonia nitrogen wastewater, and the efficiency of the subsequent activation and stripping process can be improved.
2. In the stripping process, the inventor finds that not only the pH value influences the dissociation rate of ammonia nitrogen, but also the gas content in the air influences the dissociation rate of ammonia nitrogen, the content of nitrogen in the air is improved, the ammonia can be obviously promoted to escape from the water, and meanwhile, the stripping process is divided into three stages, so that the ammonia nitrogen dissociation rate is improved, and the effects of energy conservation and consumption reduction are achieved.
In conclusion, the ammonia nitrogen wastewater is adsorbed and pre-activated by the pretreated activated carbon before ammonia activation, three-stage stripping is adopted, and a small amount of nitrogen is introduced in the process, so that the concentration of the used sodium hydroxide solution can be reduced, ammonium chloride with higher concentration can be obtained, the requirement of recycling and preparing desorption solution is met, and NH in the deaminated wastewater is removed3The N concentration and the ammonia content of the discharged waste gas meet the Integrated wastewater discharge Standard (GB 8978-1996) and the foul pollutant discharge Standard (GB 14554-93).
Detailed Description
Example 1
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 30g/L for 10m of ammonia nitrogen wastewater3Using 4kgAdsorbing and pre-activating the active carbon, and filtering;
the method comprises the following steps of (1) pretreating activated carbon: mixing 4kg of activated carbon with 80g/L sodium hydroxide solution, treating at 50 ℃ for 40 minutes, and filtering to obtain the activated carbon.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 80g/L is 1g:2 ml;
(2) pumping the filtered wastewater into a stirring tank, adding 80g/L sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100:8
(3) Introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding a sodium hydroxide solution to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, wherein 600sccm air is introduced into the first stage at 40 ℃ for 20 minutes; in the second stage, 500sccm air and 100sccm nitrogen are introduced at 70 ℃ for 20 minutes; in the third stage, 600sccm of air is introduced at the temperature of 55 ℃ for 20 minutes;
adjusting the pH value of the sodium hydroxide solution to obtain sodium hydroxide filtrate after the pretreatment of the activated carbon in the step (1);
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the concentration of hydrochloric acid is 200g/L, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main process to prepare desorption liquid.
Example 2
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 35g/L for 10m of ammonia nitrogen wastewater3Adsorbing and pre-activating with 5kg of active carbon, and filtering;
the method comprises the following steps of (1) pretreating activated carbon: mixing 5kg of active carbon with 100g/L sodium hydroxide solution, treating at 55 ℃ for 45 minutes, and filtering to obtain the active carbon.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 100g/L is 1g:5 ml;
(2) pumping the filtered wastewater into a stirring tank, adding 100g/L sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100:10
(3) Introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding sodium hydroxide solution with concentration to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, 700sccm air is introduced into the first stage at 45 ℃ for 30 minutes; in the second stage, 600sccm air and 120sccm nitrogen are introduced at 75 ℃ for 30 minutes; in the third stage, 700sccm air is introduced at the temperature of 60 ℃ for 30 minutes;
adjusting the pH value of the sodium hydroxide solution to obtain sodium hydroxide filtrate after the pretreatment of the activated carbon in the step (1);
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the concentration of hydrochloric acid is 240g/L, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main process to prepare desorption liquid.
Example 3
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 40g/L for 10m of ammonia nitrogen wastewater3Adsorbing and pre-activating with 6kg of active carbon, and filtering;
the method comprises the following steps of (1) pretreating activated carbon: mixing 6kg of active carbon with 120g/L sodium hydroxide solution, treating at 60 ℃ for 50 minutes, and filtering to obtain the active carbon.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 120g/L is 1g:8 ml;
(2) pumping the filtered wastewater into a stirring tank, adding 120g/L sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100:12
(3) Introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding sodium hydroxide solution with concentration to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, wherein 800sccm air is introduced into the first stage at the temperature of 50 ℃ for 40 minutes; in the second stage, 650sccm air and 150sccm nitrogen are introduced at 80 ℃ for 40 minutes; in the third stage, 800sccm of air is introduced at the temperature of 65 ℃ for 40 minutes;
adjusting the pH value of the sodium hydroxide solution to obtain sodium hydroxide filtrate after the pretreatment of the activated carbon in the step (1);
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the concentration of hydrochloric acid is 280g/L, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main process to prepare desorption liquid.
Example 4
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 30g/L for 10m of ammonia nitrogen wastewater3Adsorbing and pre-activating with 5kg of active carbon, and filtering;
the method comprises the following steps of (1) pretreating activated carbon: mixing 5kg of active carbon with 120g/L sodium hydroxide solution, treating at 50 ℃ for 45 minutes, and filtering to obtain the product.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 120g/L is 1g:8 ml;
(2) pumping the filtered wastewater into a stirring tank, adding 80g/L sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100:10
(3) Introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding sodium hydroxide solution with concentration to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, wherein 800sccm air is introduced into the first stage at the temperature of 40 ℃ for 30 minutes; in the second stage, 650sccm air and 100sccm nitrogen are introduced at 75 ℃ for 40 minutes; in the third stage, 600sccm of air is introduced at the temperature of 60 ℃ for 40 minutes;
adjusting the pH value of the sodium hydroxide solution to obtain sodium hydroxide filtrate after the pretreatment of the activated carbon in the step (1);
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the concentration of hydrochloric acid is 200g/L, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main process to prepare desorption liquid.
Example 5
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 35g/L for 10m of ammonia nitrogen wastewater3Adsorbing and pre-activating with 6kg of active carbon, and filtering;
the method comprises the following steps of (1) pretreating activated carbon: mixing 6kg of active carbon with 80g/L sodium hydroxide solution, treating at 55 ℃ for 50 minutes, and filtering to obtain the active carbon.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 80g/L is 1g:2 ml;
(2) pumping the filtered wastewater into a stirring tank, adding 100g/L sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100:12
(3) Introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding sodium hydroxide solution with concentration to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, wherein 600sccm air is introduced into the first stage at 45 ℃ for 40 minutes; in the second stage, 500sccm air and 120sccm nitrogen are introduced at 80 ℃ for 20 minutes; in the third stage, 700sccm air is introduced at the temperature of 65 ℃ for 20 minutes;
adjusting the pH value of the sodium hydroxide solution to obtain sodium hydroxide filtrate after the pretreatment of the activated carbon in the step (1);
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the concentration of hydrochloric acid is 240g/L, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main process to prepare desorption liquid.
Example 6
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 40g/L for 10m of ammonia nitrogen wastewater3Adsorbing and pre-activating with 4kg of active carbon, and filtering;
the method comprises the following steps of (1) pretreating activated carbon: mixing 4kg of activated carbon with 100g/L sodium hydroxide solution, treating at 60 ℃ for 40 minutes, and filtering to obtain the activated carbon.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 100g/L is 1g:5 ml;
(2) pumping the filtered wastewater into a stirring tank, adding 120g/L sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100:8
(3) Introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding sodium hydroxide solution with concentration to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, 700sccm air is introduced into the first stage at the temperature of 50 ℃ for 20 minutes; in the second stage, 600sccm air and 150sccm nitrogen are introduced at 70 ℃ for 30 minutes; in the third stage, 800sccm air is introduced at 55 ℃ for 30 minutes;
adjusting the pH value of the sodium hydroxide solution to obtain sodium hydroxide filtrate after the pretreatment of the activated carbon in the step (1);
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the concentration of hydrochloric acid is 280g/L, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main process to prepare desorption liquid.
Example 7
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 30g/L for 10m of ammonia nitrogen wastewater3Adsorbing and pre-activating with 6kg of active carbon, and filtering;
the method comprises the following steps of (1) pretreating activated carbon: mixing 6kg of active carbon with 90g/L sodium hydroxide solution, treating at 55 ℃ for 50 minutes, and filtering to obtain the active carbon.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 90g/L is 1g:4 ml;
(2) pumping the filtered wastewater into a stirring tank, adding 90g/L sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100:9
(3) Introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding sodium hydroxide solution with concentration to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, 650sccm air is introduced into the first stage, the temperature is 40 ℃, and the time is 25 minutes; in the second stage, 550sccm air and 100sccm nitrogen are introduced at 80 ℃ for 25 minutes; in the third stage, 650sccm air is introduced at 55 ℃ for 25 minutes;
adjusting the pH value of the sodium hydroxide solution to obtain sodium hydroxide filtrate after the pretreatment of the activated carbon in the step (1);
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the concentration of hydrochloric acid is 220g/L, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main process to prepare desorption liquid.
Example 8
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 40g/L for 10m of ammonia nitrogen wastewater3Adsorbing and pre-activating with 4kg of active carbon, and filtering;
the method comprises the following steps of (1) pretreating activated carbon: mixing 4kg of activated carbon with 110g/L sodium hydroxide solution, treating at 60 ℃ for 40 minutes, and filtering to obtain the activated carbon.
Wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 110g/L is 1g:6 ml;
(2) pumping the filtered wastewater into a stirring tank, adding 110g/L sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100:11
(3) Introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding sodium hydroxide solution with concentration to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, wherein 750sccm air is introduced into the first stage at the temperature of 50 ℃ for 35 minutes; in the second stage, 620sccm air and 150sccm nitrogen are introduced at 80 ℃ for 35 minutes; in the third stage, 750sccm air is introduced at 55 ℃ for 35 minutes;
adjusting the pH value of the sodium hydroxide solution to obtain sodium hydroxide filtrate after the pretreatment of the activated carbon in the step (1);
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the concentration of hydrochloric acid is 250g/L, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main process to prepare desorption liquid.
Comparative example 1 (prior art patent)
The authorization announcement is as follows: CN104310426B in example 1 of the Chinese patent "A Process for recovering Ammonia from waste gas of Ammonia Nitrogen wastewater from tungsten metallurgy", 150g/L sodium hydroxide is used for activation, the concentration of sodium hydroxide is higher than that of sodium hydroxide used in the invention, and finally ammonium chloride with the concentration of 190g/L is obtained. The wastewater after deamination is discharged into a tungsten recovery system for treatment and then enters a sewage treatment station for dilution treatment, the concentration of NH3-N is 14.15mg/L, and the content of ammonia in discharged waste gas is NH3 which is less than or equal to 1.24mg/m3。
Comparative example 2 (direct ammonia activation without addition of activated carbon)
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) for ammonia nitrogen wastewater with ammonia nitrogen concentration of 30g/L being 10m3Carrying out direct filtration;
the rest of the procedure was the same as in example 1.
Comparative example 3 (activated carbon not pretreated)
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(1) in a clarification tank, the concentration of ammonia nitrogen is 35g/L for 10m of ammonia nitrogen wastewater3Adsorbing with 5kg of non-pretreated active carbon, and filtering;
the rest of the procedure was the same as in example 2.
Comparative example 4 (ordinary stripping process)
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(3) introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding a sodium hydroxide solution with the concentration of 11, adjusting the pH value to be 11, introducing 800sccm air, and stripping at the temperature of 80 ℃ for 120 minutes;
the rest of the procedure was the same as in example 3.
Comparative example 5 (three-stage stripping Process without Nitrogen)
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(3) introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding sodium hydroxide solution with concentration to adjust the pH value to 11, and stripping;
the stripping is divided into three stages, wherein 800sccm air is introduced into the first stage at the temperature of 40 ℃ for 30 minutes; in the second stage, 650sccm air is introduced at 75 ℃ for 40 minutes; in the third stage, 600sccm of air is introduced at the temperature of 60 ℃ for 40 minutes;
the rest of the procedure was the same as in example 4.
Comparative example 6 (direct stripping Process with Nitrogen gas)
A method for recycling ammonium chloride in the APT production process comprises the following specific steps:
(3) introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding a sodium hydroxide solution with the concentration of adjusting the pH value to 11, introducing 500sccm air and 120sccm nitrogen, and stripping at the temperature of 80 ℃ for 80 minutes;
the rest of the procedure was the same as in example 5.
The present invention is not limited to the above-described embodiments, and various changes may be made by those skilled in the art, and any changes equivalent or similar to the present invention are intended to be included within the scope of the claims.
The contents of ammonium chloride and waste water and exhaust gas obtained in each example and comparative example are shown in the following table.
TABLE 1 ammonium chloride content, waste water and waste gas content obtained in each example and comparative example
As can be seen from the data in the above table, examples 1-8 of the present invention produced higher concentrations of ammonium chloride and wastewater NH3The effects are better than those of comparative example 1 (prior art patent), comparative example 2 (direct ammonia activation without activated carbon), comparative example 3 (activated carbon is not pretreated), comparative example 4 (normal stripping process), comparative example 5 (three-stage stripping process without nitrogen), and comparative example 6 (direct stripping process with nitrogen), especially the best effect of example 2. It can be seen that the ammonia nitrogen wastewater is firstly adsorbed and preactivated by pretreated activated carbon before ammonia activation, three-stage stripping is adopted, a small amount of nitrogen is introduced in the process to obtain the concentration of ammonium chloride, and NH in the deaminated wastewater3The concentration of-N and the ammonia content of the discharged waste gas have influence, so the invention firstly adsorbs and preactivates the ammonia nitrogen wastewater by the pretreated activated carbon before the ammonia activation, adopts a three-stage stripping process, and introduces a small amount of nitrogen in the stripping process to realize combined action, thereby not only reducing the used hydrogen hydroxideThe concentration of the sodium solution is higher to obtain ammonium chloride with higher concentration, and wastewater NH after deamination3The N concentration and the ammonia content of the discharged waste gas are lower, and the method meets the integrated wastewater discharge standard (GB 8978-1996) and the malodorous pollutant discharge standard (GB 14554-93).
Claims (8)
1. A method for recycling ammonium chloride in the APT production process is characterized in that: the method comprises the following specific steps:
(1) adsorbing and pre-activating ammonia nitrogen wastewater by using activated carbon in a clarification tank, and filtering;
(2) pumping the filtered wastewater into a stirring tank, adding a sodium hydroxide solution for ammonia activation, and adjusting the pH value to 10-11;
(3) introducing the wastewater after ammonia activation and ammonia gas generated by ammonia activation into a stripping tower, adding a sodium hydroxide solution to adjust the pH value to 11, and stripping;
(4) after ammonia nitrogen wastewater is blown off, the generated ammonia-containing gas and ammonia gas which is not condensed by a steam-water separator enter a hydrochloric acid spray tower for cyclic absorption, the pH value is adjusted to 6.5-7, and ammonium chloride is prepared and returned to the main flow to prepare desorption liquid;
in the step (1), the activated carbon is pretreated, and the specific pretreatment method comprises the following steps: mixing activated carbon with 80-120g/L sodium hydroxide solution, treating at 50-60 deg.C for 40-50 min, and filtering;
in the step (3), the stripping is divided into three stages, wherein air is introduced into the first stage at the temperature of 40-50 ℃ for 20-40 minutes; in the second stage, air and nitrogen are introduced at the temperature of 70-80 ℃ for 20-40 minutes; in the third stage, air is introduced at 55-65 deg.C for 20-40 min.
2. The method for recycling ammonium chloride in the APT production process according to claim 1, which is characterized in that:
wherein the feed-liquid ratio of the activated carbon to the sodium hydroxide solution with the concentration of 80-120g/L is 1g:2-8 ml.
3. The method for recycling ammonium chloride in the APT production process according to claim 1, which is characterized in that:
in the step (1), the feed-liquid ratio of the ammonia nitrogen wastewater to the activated carbon is 1L:0.4-0.6 g.
4. The method for recycling ammonium chloride in the APT production process according to claim 1, which is characterized in that:
in the step (2), the concentration of the sodium hydroxide solution is 80-120 g/L.
5. The method for recycling ammonium chloride in the APT production process according to claim 1, which is characterized in that:
in the step (2), the volume ratio of the filtered wastewater to the sodium hydroxide solution is 100: 8-12.
6. The method for recycling ammonium chloride in the APT production process according to claim 1, which is characterized in that:
wherein, the air flow introduced in the first and the third stages is as follows: 600-; the air flow introduced in the second stage is as follows: 500-650sccm, nitrogen flow rate: 100-.
7. The method for recycling ammonium chloride in the APT production process according to claim 1, which is characterized in that:
in the step (3), the sodium hydroxide solution used for adjusting the pH value is the sodium hydroxide filtrate obtained after the pretreatment of the activated carbon in the step (1).
8. The method for recycling ammonium chloride in the APT production process according to claim 1, which is characterized in that:
in the step (4), the concentration of the hydrochloric acid is 200-280 g/L.
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| JP4391879B2 (en) * | 2004-05-07 | 2009-12-24 | バブコック日立株式会社 | Ammonia decomposition and removal equipment |
| CN101531425B (en) * | 2009-04-08 | 2011-12-07 | 赛普（无锡）膜科技发展有限公司 | Method for treating ammonia nitrogen wastewater |
| CN104310426B (en) * | 2014-10-09 | 2016-06-08 | 中国有色集团（广西）平桂飞碟股份有限公司 | A kind of technique reclaiming ammonia from Tungsten smelting ammonia nitrogen waste water waste gas |
| CN105110545B (en) * | 2015-09-25 | 2017-07-04 | 浙江奇彩环境科技股份有限公司 | The handling process of double cyanogen waste water in disperse blue 60 production process |
| CN106430244B (en) * | 2016-11-08 | 2019-05-31 | 南京大学 | A method of it is recycled from ammonia nitrogen waste water and purifies ammonia |
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2018
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