CN115818882A - Method and system for recycling acidic ammonium sulfate waste liquid - Google Patents
Method and system for recycling acidic ammonium sulfate waste liquid Download PDFInfo
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- CN115818882A CN115818882A CN202211575729.2A CN202211575729A CN115818882A CN 115818882 A CN115818882 A CN 115818882A CN 202211575729 A CN202211575729 A CN 202211575729A CN 115818882 A CN115818882 A CN 115818882A
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Abstract
The application provides a recovery processing method of acid ammonium sulfate waste liquid, for this reason, this application still provides the recovery processing system of acid ammonium sulfate waste liquid, and its reducible equipment corrodes, introduces metallic impurity when avoiding the waste liquid to handle, still can prevent that pipeline and equipment from taking place to block up, improves the quality and the production efficiency of retrieving the result, guarantees production safety, reduces the degree of difficulty and the frequency of artifical desilting. Adding an alkaline solution and an acidic ammonium sulfate waste liquid into a pretreatment kettle for neutralization pretreatment, and adding a remover for oxidative decomposition of hydrogen peroxide; the pretreated materials enter a triple-effect evaporator for evaporation and concentration, and the pretreated materials are also used as flushing liquid for flushing the triple-effect evaporator; the concentrated material is primarily separated by a cyclone separator and enters a crystallizer, then ammonium sulfate finished products are obtained by crystallization, centrifugal separation and drying, and separated mother liquor and centrifugal mother liquor are respectively reused in the three-effect evaporator.
Description
Technical Field
The application relates to the technical field of industrial wastewater treatment, in particular to a method and a system for recovering and treating acidic ammonium sulfate waste liquid.
Background
In the production process of semiconductor and electronic industries, a large amount of wastewater containing high ammonia nitrogen and sulfuric acid waste liquid containing hydrogen peroxide are generated, and in order to better store or perform resource utilization, production enterprises can perform primary treatment on the waste liquid, for example, the high ammonia nitrogen wastewater is separated through a stripping process, and the generated ammonia-containing waste gas enters an absorption tower and is absorbed by the sulfuric acid waste liquid containing hydrogen peroxide, so that acidic ammonium sulfate waste liquid with the concentration of 20-40% and containing a small amount of hydrogen peroxide and free acid is generated.
The traditional treatment mode of the ammonium sulfate waste liquid is to obtain a solid ammonium sulfate product through evaporation, crystallization and centrifugal drying after acid-base neutralization, however, the acidic ammonium sulfate waste liquid obtained through primary treatment of the waste liquid in the semiconductor and electronic industries contains hydrogen peroxide, and during evaporation, equipment is easily corroded by the hydrogen peroxide, so that metal ion impurities are introduced, the quality of the finished ammonium sulfate product is influenced, and the service life of the equipment is shortened; in addition, for the acidic ammonium sulfate waste liquid with 20wt% -40 wt% of ammonium sulfate, the influence of the ammonium sulfate solubility saturation is generated in the evaporation process, and the concentrated ammonium sulfate solution is easy to generate crystals and gather, so that the blockage of evaporation equipment and pipelines is caused, the production efficiency and the production safety are influenced, and the manual dredging is troublesome.
Disclosure of Invention
When carrying out acid ammonium sulfate waste liquid treatment to current ammonium sulfate waste liquid treatment method, easily cause equipment corrosion, influence finished product quality and equipment life, and evaporating line and equipment are easy to be blockked up, influence production efficiency and production safety, the difficult problem of artifical desilting, this application provides a recovery processing method of acid ammonium sulfate waste liquid, for this reason, this application still provides the recovery processing system of acid ammonium sulfate waste liquid, its reducible equipment corrosion, introduce metallic impurity when avoiding the waste liquid to handle, still can prevent that pipeline and equipment from taking place to block up, improve the quality and the production efficiency of recovery product, guarantee production safety, reduce the degree of difficulty and the frequency of artifical desilting.
The technical scheme is as follows: a method for recovering and treating acidic ammonium sulfate waste liquid comprises the following steps,
s1: adding an alkaline solution and the acidic ammonium sulfate waste liquid into a pretreatment kettle for neutralization pretreatment;
s2: the pretreated materials enter a triple-effect evaporator for evaporation and concentration;
s3: the concentrated material enters a crystallizer for crystallization;
s4: the crystallized materials enter a centrifugal machine for centrifugal separation;
s5: drying the crystal obtained by centrifugal separation in a dryer to obtain an ammonium sulfate finished product, and reusing the mother liquor in the triple-effect evaporator;
the method is characterized in that: in S1, after neutralization pretreatment is carried out until the pH value is 5-7, a remover for oxidative decomposition of hydrogen peroxide is added, wherein the molar ratio of hydrogen peroxide to the remover is 1-1.5; in S2, the pretreated material is also used as a flushing fluid to flush the triple-effect evaporator; and S3, performing primary separation on the concentrated material through a cyclone separator before the concentrated material enters the crystallizer.
It is further characterized in that:
in S1, neutralizing and pretreating acidic ammonium sulfate waste liquid containing 20-40 wt% of ammonium sulfate, 0.1-4 wt% of free acid and 0.1-8 wt% of hydrogen peroxide at 50-70 ℃ under normal pressure; the alkali liquor is 10 to 30 weight percent of ammonia water;
the remover is an ammonium salt remover;
in S2, evaporating and concentrating under-0.06 Mpa to-0.08 Mpa and at 80-100 ℃; the solid content of the liquid phase of the evaporated and concentrated material is 10-25% (V/V); and in S2, after the concentrated material is discharged, washing for 20S after the operation is carried out for 4-8 min and the material is discharged for 60S.
The utility model provides a recovery processing system of acid ammonium sulfate waste liquid, its includes the preliminary treatment cauldron, the triple effect evaporimeter, crystallizer, centrifuge and the desiccator that connect in order, its characterized in that: the pretreatment kettle is connected with an acidic ammonium sulfate waste liquid pipeline, an alkali liquid pipeline and a remover pipeline respectively, and is also communicated with the triple-effect evaporator through a material washing branch pipeline, and a cyclone separator is arranged between the triple-effect evaporator and the crystallizer.
It is further characterized in that:
the triple-effect evaporator is connected with a water washing pipeline;
the crystallizer is provided with a stirrer, a guide cylinder is sleeved on the stirrer, and baffling baffles are arranged on the crystallizer on two sides of the stirrer; a gap is formed between the baffling baffle and the inner wall of the crystallizer;
the water flushing pipeline is communicated with the first-effect separator in the three-effect evaporator through a first flushing pipeline, is communicated with the second-effect separator in the three-effect evaporator through a second flushing pipeline, and is communicated with the third-effect separator in the three-effect evaporator through a third flushing pipeline; the material flushing branch pipeline is communicated with the first flushing pipeline;
the two-effect separator and the three-effect separator are respectively communicated with the crystallizer through the cyclone separator; the two-effect separator and the three-effect separator also form a loop with the cyclone separator respectively;
the centrifuge is communicated with the triple-effect evaporator through a temporary storage tank.
The beneficial effect of this application is:
(1) The excessive remover is added to oxidize and decompose the hydrogen peroxide, and the hydrogen peroxide is removed in the pretreatment stage, so that metal equipment in the subsequent treatment process can be prevented from being corroded, metal ion impurities are prevented from being introduced, the product quality is improved, and the service life of the equipment is prolonged;
(2) After the materials are discharged for a period of time, the pretreated raw materials are used as flushing liquid through the material flushing branch pipeline, or the pretreated raw materials are diluted through the water flushing pipeline and the material flushing branch pipeline and then are used as flushing liquid to flush the triple-effect evaporator, so that crystals generated during evaporation and concentration of an ammonium sulfate solution can be prevented from being accumulated to block the pipeline; meanwhile, condensed water or pressurized water of materials can be independently and periodically used for washing the triple-effect evaporator and the process pipeline through the water washing pipeline, so that ammonium sulfate crystals are further prevented from being gathered to block the pipeline, the quality and the production efficiency of recovered products are improved, the production safety is ensured, the difficulty and the frequency of manual dredging are reduced, and the utilization effect of the materials can be improved;
(3) Through the cyclone separator who connects triple effect evaporimeter and crystallizer, not only can carry out primary separation to material solid-liquid, reduce the moisture of crystal, improve the crystallization effect of crystallizer and the finished purity of ammonium sulfate, can also retrieval and utilization separation mother liquor, improve the rate of recovery of ammonium sulfate.
In addition, through agitator, draft tube and baffling baffle in the crystallizer, under the promotion of agitator, the suspension can form major diameter granule ammonium sulfate at the draft tube and the passageway inner loop crystallization between draft tube and the baffling baffle with higher speed, improves crystallization efficiency, still can prevent that dusting, caking when follow-up drying from influencing the recovery article quality of ammonium sulfate.
Drawings
FIG. 1 is a process flow diagram of the present application.
FIG. 2 is a schematic diagram of a process system according to the present application;
FIG. 3 is an enlarged schematic view of the structure at A in FIG. 2;
fig. 4 is an enlarged schematic view of a portion B in fig. 2.
Detailed Description
The present application is further described with reference to the accompanying drawings in which:
the application provides a method for recovering and treating acidic ammonium sulfate waste liquid, which comprises the following steps,
s1: pretreatment of
Adding alkali liquor and acidic ammonium sulfate waste liquid of 20-40 wt% of ammonium sulfate, 0.1-4 wt% of free acid and 0.1-8 wt% of hydrogen peroxide into a pretreatment kettle 1 at normal pressure and 50-70 ℃ for neutralization pretreatment; the alkali liquor is 10wt% -30 wt% ammonia water; after neutralization pretreatment is carried out until the pH value is 5-7, a remover for oxidative decomposition of hydrogen peroxide is added, and the molar ratio of hydrogen peroxide to the remover is 1-1.5; the remover is an ammonium salt remover, preferably, the remover is ammonium sulfite, so that new impurities can be prevented from being introduced, and the recovery purity and recovery rate of the ammonium sulfate are improved.
S2: concentrating by evaporation
The pretreated materials enter a triple-effect evaporator, and are evaporated and concentrated under the pressure of-0.06 MPa to-0.08 MPa and the temperature of 80 ℃ to 100 ℃; the solid content of the liquid phase of the material after evaporation and concentration is 10-25% (V/V); the pretreated material is also used as a washing liquid, after a period of discharging, the three-effect evaporator is washed through the material washing branch 2902, preferably, when the material after evaporation concentration reaches the discharging concentration, namely the content of ammonium sulfate is more than or equal to 40%, the three-effect evaporator is washed for 20s through the material washing branch 2902 after the operation is carried out for 4-8 min and the discharging is carried out for 60s, so that the blockage of evaporation equipment and evaporation pipelines can be effectively prevented.
S3: separation of crystals
The concentrated material is primarily separated by a cyclone separator 8 and then enters a crystallizer 9 for crystallization.
S4: centrifugal separation
The crystallized material is fed into a centrifuge 10 for centrifugal separation.
S5: the crystal obtained by centrifugal separation enters a drier for drying to obtain an ammonium sulfate finished product, and the mother liquor is reused in the triple-effect evaporator.
As shown in fig. 2 to 4, the present application further provides a system for recovering and treating an acidic ammonium sulfate waste liquid, which comprises a pretreatment kettle 1, a triple-effect evaporator, a crystallizer 9, a centrifuge 10 and a dryer, which are connected in sequence, preferably, the pretreatment kettle 1 is a jacketed stirred tank reactor, a first stirring paddle 101 is installed in the kettle, and a jacket 102 is installed outside the kettle, so that a reaction temperature error can be reduced, and the reaction can be performed uniformly and safely; the pretreatment kettle 1 is respectively connected with an acidic ammonium sulfate waste liquid pipeline 12, an alkali liquid pipeline 13 and a remover pipeline 14, the pretreatment kettle 1 is also communicated with a triple-effect evaporator through a material washing branch pipeline 2902, and a cyclone separator is arranged between the triple-effect evaporator and the crystallizer 9; the triple-effect evaporator is connected with a water flushing pipeline 16, the water flushing pipeline 16 is communicated with a first-effect separator 2 in the triple-effect evaporator through a first flushing pipeline 1601, is communicated with a second-effect separator 4 in the triple-effect evaporator through a second flushing pipeline 1602, and is communicated with a triple-effect separator 6 in the triple-effect evaporator through a third flushing pipeline 1603.
Preferably, as shown in fig. 1 and 4, the material flushing branch pipe 2902 is a branch of the material conveying pipe 29 which communicates the pretreatment kettle 1 with the first effect separator 2 in the three-effect evaporator, the material flushing branch pipe 2902 communicates with the first flushing pipe 1601 and is connected to the first effect separator 2 from the top through the first flushing pipe 1601, and the pretreated material enters the first effect separator 2 in the three-effect evaporator through the main pipe 2901 of the material conveying pipe 29 in a downstream manner to be evaporated and concentrated; as a flushing liquid, the pretreated material enters the first-effect separator 2 through the material flushing branch pipeline 2902 in a downstream mode to flush the evaporation equipment and the pipeline by controlling the opening and closing of the valve 36, or enters the first-effect separator 2 through the first flushing pipeline 1601 of the flushing pipeline 16 after being mixed with material condensate water or pressurized water to flush the evaporation equipment and the pipeline, so that crystals generated during evaporation and concentration of an ammonium sulfate solution can be prevented from being accumulated to block the pipeline; meanwhile, the pipeline 16 can be independently flushed through the first flushing pipeline 1601, the second flushing pipeline 1602 and the third flushing pipeline 1603 respectively to periodically flush the triple-effect evaporator and the process pipeline by using condensed water or pressurized water of the materials, so that the ammonium sulfate crystals are further prevented from being accumulated to block the pipeline, the quality and the production efficiency of recovered products are improved, the production safety is ensured, the difficulty and the frequency of manual dredging are reduced, and the utilization effect of the materials can be improved.
As shown in fig. 2, the first-effect separator 2, the second-effect separator 4 and the third-effect separator 6 in the three-effect evaporator are respectively connected with the first-effect heater 3, the second pipeline 25 is connected with the second-effect heater 5 and the third pipeline 23 is connected with the third-effect heater 7 through the first pipeline 27, so that a first-effect internal circulation pipeline, a second-effect internal circulation pipeline and a third-effect internal circulation pipeline are formed, the evaporation concentration effect is improved, and the loss of ammonium sulfate recovered products is reduced; preferably, the shell pass of the first-effect heater 3 is connected with steam through a first steam pipeline, the steam evaporated by the first-effect separator 2 can be used as a heat source of the second-effect heater 5 and connected with the shell pass of the second-effect heater 5 through a second steam pipeline 34, the steam evaporated by the second-effect separator 4 can be used as a heat source of the third-effect heater 7 and connected with the shell pass of the third-effect heater 7 through a branch 3501 of a third steam pipeline 35, the steam evaporated by the third-effect separator 6 can be used as a heat source of the pretreatment kettle 1 and connected with the jacket 102 of the pretreatment kettle 1 through a fourth steam pipeline 15, and under the working condition that the third-effect separator 6 is not started, the steam evaporated by the second-effect separator 4 can also be used as a heat source of the pretreatment kettle 1 and connected with the fourth steam pipeline 15 through a branch 3502 of the third steam pipeline 35 so as to be introduced into the jacket 102 of the treatment kettle 1, so that the utilization efficiency of the energy sources of the recovery treatment system can be improved, the use amount of the steam outside the treatment system can be reduced, and the use amount of the steam outside the treatment system can be effectively reduced.
Preferably, the first-effect separator 2 in the three-effect evaporator is communicated with the second-effect separator 4 through a first branch 2801 of the first-effect evaporation pipeline 28, and is communicated with the third-effect separator 6 through a second branch 2802 of the first-effect evaporation pipeline 28, so as to form a structure that the second-effect separator 4 and the third-effect separator 6 are connected in parallel, and waste liquid treatment can be performed by opening the first-effect separator 2 and the second-effect separator 4 in the three-effect evaporator and the first-effect internal circulation pipeline and the second-effect internal circulation pipeline which are respectively connected, or opening the first-effect separator 2, the second-effect separator 4 and the third-effect separator 6 in the three-effect evaporator and the first-effect internal circulation pipeline, the second-effect internal circulation pipeline and the third-effect internal circulation pipeline which are respectively connected, so as to conveniently meet waste liquid treatment requirements of different working conditions, save energy and reduce consumption.
As shown in fig. 2 and fig. 3, the crystallizer 9 is provided with a stirrer 901, the stirrer 901 is sleeved with a guide cylinder 902, baffling baffles 903 are installed on the crystallizer 9 on two sides of the stirrer 901, a gap is formed between the baffling baffles 903 and the inner wall of the crystallizer 9, under the pushing of the stirrer, the suspension can be circularly crystallized in the guide cylinder and a channel between the guide cylinder and the baffling baffles, large-diameter particle ammonium sulfate is formed in an accelerating manner, the crystallization efficiency is improved, and dust and agglomeration during subsequent drying can be prevented from affecting the quality of the recovered ammonium sulfate; preferably, the stirrer 901 is a push type stirring paddle, is simple and convenient to operate, runs stably, can realize uniform stirring, and is helpful to promote the suspension to be circularly crystallized in the crystallizer.
As shown in fig. 2 and 3, the two-effect separator 4 is connected with one cyclone separator 8a through a two-effect evaporation pipeline 19, the three-effect separator 6 is connected with the other cyclone separator 8b through a three-effect evaporation pipeline 24, and cone bottom outlets of the two cyclone separators 8a and 8b are respectively communicated with the crystallizer 9, so that solid and liquid of the material can be primarily separated, the water content of crystals is reduced, and the crystallization effect of the crystallizer and the purity of ammonium sulfate finished products are improved; the secondary-effect separator 4 and the tertiary-effect separator 6 also form loops with the cyclone separator respectively, namely, a separation mother liquor outlet of the cyclone separator 8a is connected with the secondary-effect separator 4 through a first recycling pipeline 17, and a separation mother liquor outlet of the cyclone separator 8b is connected with the tertiary-effect separator 6 through a second recycling pipeline 18, so that the separation mother liquor is recycled for the tertiary-effect evaporator, and the recovery rate of resource products is improved; preferably, the first recycling pipeline 17 is further communicated with the water washing pipeline 16 through a pipeline 37 and the second recycling pipeline 18 through a pipeline 38, and the separated mother liquor can be washed if the concentration of the recycled separated mother liquor is higher, so that the pipeline is prevented from being blocked when the separated mother liquor is recycled and separated out and crystallized.
As shown in fig. 2, the centrifuge 10 is communicated with the triple-effect evaporator through the temporary storage tank 11 and the third recycling pipeline 22, preferably, an outlet of the temporary storage tank 11 is communicated with the third-effect internal circulation pipeline through a first branch 2201 of the third recycling pipeline 22, that is, the first branch 2201 of the third recycling pipeline is connected with the third pipeline 23, and is communicated with the first-effect separator 2 through a second branch 2202 of the third recycling pipeline 22, that is, the second branch 2202 of the third recycling pipeline is connected with the material conveying pipeline 29, so that the centrifugal mother liquor can be recycled in the triple-effect evaporator through the first branch 2201 and the second branch 2202 respectively under different working conditions, and the recovery rate of the resource product is further improved. Because the temperature difference exists between the centrifugal mother liquor and the materials in the evaporation system after the materials are subjected to centrifugal separation after evaporation concentration, the larger the temperature difference is, the more the heat loss of the materials is caused according to the heat transfer law, when the first-effect separator 2, the second-effect separator 4 and the third-effect separator 6 in the three-effect evaporator are all opened, the steam evaporated by the second-effect separator 4 is used as the heat source of the three-effect heater 7, so the temperature in the third-effect separator 6 is lower than that in the second-effect separator 4, the centrifugal mother liquor is recycled to the third-effect internal circulation pipeline through the temporary storage tank 11 and the first branch 2201 of the third recycling pipeline 22, the heat loss can be reduced, the heat recovery efficiency is improved, the production cost is reduced, and meanwhile, the energy is further saved.
Preferably, the material crystallized in the crystallizer 9 enters the centrifuge 10 through the connecting pipeline 21, the crystal obtained by centrifugal separation enters the dryer, the dried finished ammonium sulfate product enters the automatic packaging system 26, and the dryer and the automatic packaging system 26 can be controlled by an automatic program to detect, weigh and package the dried finished ammonium sulfate product, so that the transportation and sale of the recovered product are facilitated, and the resource recycling is realized.
In FIG. 2, 31 is a feed pump and 32 is a forced circulation pump; the vacuum pump 20 respectively vacuumizes the first effect separator 2, the second effect separator 4 and the third effect separator 6 of the three-effect evaporator through a first branch 3001, a second branch 3002 and a third branch 3003 of the connecting pipeline 30, and provides negative pressure reaction conditions for evaporation and concentration; preferably, as shown in fig. 2 and 3, the pipelines for transporting materials, such as the first-effect evaporation pipeline 28, the second-effect evaporation pipeline 19, and the third-effect evaporation pipeline 24, the first pipeline 27, the second pipeline 25, and the third pipeline 23 forming the first-effect internal circulation pipeline, the second-effect internal circulation pipeline, and the third-effect internal circulation pipeline, the material transportation pipeline 29, the fourth steam pipeline 15, the first steam pipeline, the second steam pipeline 34, the third steam pipeline 35, the connecting pipeline 21, and the third recycling pipeline 22 are respectively coated with an insulating layer 33, and as shown in fig. 3, the insulating layers 33 are not all shown, which is indicated by insulating layer sections, so that heat loss can be reduced, and material crystallization can be prevented from blocking the pipelines.
Example 1:
pumping 100 t of acidic ammonium sulfate waste liquid containing 20wt% of ammonium sulfate, 1 wt% of free acid and 1 wt% of hydrogen peroxide from a raw material storage tank into a pretreatment kettle 1 with a first stirring paddle 101, adding 30 wt% of ammonia water for neutralization until the pH value is 5, adding ammonium sulfite according to a molar ratio of 1.5 of hydrogen peroxide to ammonium sulfite, and oxidatively decomposing the hydrogen peroxide; preferably, the ammonium sulfite is prepared into a 5% ammonium sulfite solution for addition, so that the reaction speed and the addition amount of the chemical agent can be conveniently controlled.
The reaction solution can be preheated through the heat exchange of the steam conveyed from the triple-effect evaporator in the jacket 102 of the pretreatment kettle 1, the steam after the heat exchange is called condensed water and is discharged from a condensed water pipeline, and the condensed water pipeline can also be connected with a water washing pipeline 16 for washing liquid of evaporation equipment and pipelines, so that the resource utilization effect is improved, and the energy consumption is reduced; the pretreated materials flow downstream through a feed pump 31 and enter a three-effect evaporator for continuous decompression evaporation, wherein a first-effect separator 2, a second-effect separator 4, a third-effect separator 6, a first-effect internal circulation pipeline, a second-effect internal circulation pipeline and a third-effect internal circulation pipeline which are connected with each other are all opened, the evaporation concentration temperature is 80 ℃, the pressure is-0.08 Mpa, discharging is started when the solid content of a liquid phase of the materials after evaporation concentration is 10% (V/V), flushing is carried out after discharging, namely, the discharging 60s is carried out for 20s through a material flushing branch 2902 every 8min, and the flushing liquid is the pretreated materials and has the ammonium sulfate concentration of 25%.
Discharging after concentration, conveying a liquid phase ammonium sulfate solution with solid content of 10% (V/V) through an evaporation pipeline with a heat-insulating layer 33, keeping a flowing state, entering a crystallizer 9 through a cyclone separator for circulating crystallization for 20 min, then performing centrifugal separation, drying and automatic packaging, and recovering to obtain sulfuric acid which meets the standard requirement (see Table I) of HG/T5744-2020 industrial ammonium sulfate and has a product weight of about 19.8T; the centrifugal mother liquor is reused in the three-effect evaporator through the temporary storage tank 11 via the first branch 2201 of the third recycling pipeline 22, and impurities in the centrifugal mother liquor are accumulated in the temporary storage tank 11 to a certain extent and are periodically discharged.
Example 2:
pumping 50 t of acidic ammonium sulfate waste liquid containing 30 wt% of ammonium sulfate, 0.9 wt% of free acid and 2 wt% of hydrogen peroxide into a pretreatment kettle 1 with a first stirring paddle 101 from a raw material storage tank, adding 20wt% of ammonia water to neutralize until the pH value is 6, adding ammonium sulfite according to a molar ratio of 1.2 of hydrogen peroxide to ammonium sulfite, and carrying out oxidative decomposition on hydrogen peroxide, preferably, preparing 5% of ammonium sulfite solution from ammonium sulfite for adding, so that the reaction speed and the addition amount of a medicament can be conveniently controlled.
The reaction solution can be preheated by the heat exchange of the steam conveyed from the triple-effect evaporator in the jacket 102 of the pretreatment kettle 1, and the steam after the heat exchange is called as condensed water and is discharged from a condensed water pipeline; the pretreated materials flow downstream through a feed pump 31 and enter a three-effect evaporator for continuous decompression evaporation, wherein a first-effect separator 2, a second-effect separator 4, a third-effect separator 6, a first-effect internal circulation pipeline, a second-effect internal circulation pipeline and a third-effect internal circulation pipeline which are connected with each other are all opened, the evaporation concentration temperature is 90 ℃, the pressure is-0.07 Mpa, discharging is started when the solid content of a liquid phase of the evaporated and concentrated materials is 15% (V/V), flushing is carried out after discharging, namely, the discharging time is 6 min after operation, the discharging time is 60s, the three-effect evaporator is flushed for 20s through a material flushing branch 2902, the flushing liquid is the pretreated materials, the ammonium sulfate concentration is 35%, or the three-effect evaporator is flushed through a first flushing pipeline 1601 after a material condensate water or pressurized water mixed and diluted solution is used.
Discharging after concentration, conveying a liquid phase ammonium sulfate solution with the solid content of 15% (V/V) through an evaporation pipeline with a heat-insulating layer 33, keeping the flow state, entering a crystallizer 9 through a cyclone separator for circulating crystallization for 15 min, then performing centrifugal separation, drying and automatic packaging, and recovering to obtain sulfuric acid which meets the standard requirement (see Table I) of HG/T5744-2020 industrial ammonium sulfate and has the weight of about 14.9T according to the product; the centrifugal mother liquor is reused in the three-effect evaporator through the temporary storage tank 11 via the first branch 2201 of the third recycling pipeline 22, and impurities in the centrifugal mother liquor are accumulated in the temporary storage tank 11 to a certain extent and are periodically discharged.
Example 3:
pumping 100 t of acidic ammonium sulfate waste liquid containing 40 wt% of ammonium sulfate, 0.8 wt% of free acid and 3 wt% of hydrogen peroxide from a raw material storage tank into a pretreatment kettle 1 with a first stirring paddle 101, adding 10wt% of ammonia water to neutralize until the pH value is 7, adding ammonium sulfite according to a molar ratio of 1.5 of hydrogen peroxide to ammonium sulfite, and oxidizing and decomposing hydrogen peroxide, preferably, preparing 5% of ammonium sulfite solution from ammonium sulfite for adding, so that the reaction speed and the addition amount of a medicament can be conveniently controlled.
The reaction solution can be preheated by the heat exchange of the steam conveyed from the triple-effect evaporator in the jacket 102 of the pretreatment kettle 1, and the steam after the heat exchange is called as condensed water and is discharged from a condensed water pipeline; the pretreated material enters a three-effect evaporator through a feed pump 31 downstream for continuous reduced pressure evaporation, wherein only a first-effect separator 2 and a second-effect separator 4, as well as a first-effect internal circulation pipeline and a second-effect internal circulation pipeline which are respectively connected with the first-effect separator and the second-effect separator are started due to the high initial treatment concentration of the acidic ammonium sulfate waste liquid, the evaporation concentration temperature is 100 ℃, the pressure is-0.06 Mpa, the material starts to be discharged when the solid content of the liquid phase of the material after evaporation concentration is 20% (V/V), and is washed after discharging, namely, the discharging time is 60s every 4 min of operation, the three-effect evaporator is washed for 20s through a first washing pipeline 1601, and the ammonium sulfate concentration of the pretreated material is 45%, so the washing liquid is a solution prepared by mixing and diluting the pretreated material with condensed water, pressurized water or condensed water and pressurized water.
Discharging after concentration, conveying a liquid phase ammonium sulfate solution with the solid content of 20% (V/V) through an evaporation pipeline with a heat-insulating layer 33, keeping the flow state, entering a crystallizer 9 through a cyclone separator for circulating crystallization for 10 min, then performing centrifugal separation, drying and automatic packaging, and recovering to obtain sulfuric acid which meets the standard requirement (see Table I) of HG/T5744-2020 industrial ammonium sulfate and has the yield of about 49.8T; the centrifugal mother liquor is recycled in the triple-effect evaporator through the temporary storage tank 11 through a second branch 2202 of the third recycling pipeline, and impurities in the centrifugal mother liquor are accumulated in the temporary storage tank 11 to a certain degree and are periodically discharged.
Claims (10)
1. A method for recovering and treating acidic ammonium sulfate waste liquid comprises the following steps,
s1: adding an alkaline solution and an acidic ammonium sulfate waste solution into a pretreatment kettle for neutralization pretreatment;
s2: the pretreated materials enter a triple-effect evaporator for evaporation and concentration;
s3: the concentrated material enters a crystallizer for crystallization;
s4: the crystallized materials enter a centrifugal machine for centrifugal separation;
s5: drying the crystal obtained by centrifugal separation in a dryer to obtain an ammonium sulfate finished product, and reusing the mother liquor in the triple-effect evaporator;
the method is characterized in that: in the S1, after neutralization pretreatment is carried out until the pH value is 5-7, a remover for oxidative decomposition of hydrogen peroxide is added, wherein the molar ratio of the hydrogen peroxide to the remover is 1-1.5; in S2, the pretreated material is also used as a flushing fluid to flush the triple-effect evaporator; and S3, performing primary separation on the concentrated material through a cyclone separator before the concentrated material enters the crystallizer.
2. The method for recovering and treating the acidic ammonium sulfate waste liquid as claimed in claim 1, which is characterized in that: in S1, neutralizing and pretreating acidic ammonium sulfate waste liquid containing 20-40 wt% of ammonium sulfate, 0.1-4 wt% of free acid and 0.1-8 wt% of hydrogen peroxide at 50-70 ℃ under normal pressure; the alkali liquor is 10wt% -30 wt% of ammonia water.
3. The method for recovering and treating the acidic ammonium sulfate waste liquid as claimed in claim 1, which is characterized in that: the remover is an ammonium salt remover.
4. The method for recovering and treating the acidic ammonium sulfate waste liquid as claimed in claim 1, characterized in that: in S2, evaporating and concentrating under-0.06 Mpa to-0.08 Mpa and at 80-100 ℃; the solid content of the liquid phase of the evaporated and concentrated material is 10-25% (V/V); and in S2, after the concentrated material is discharged, washing for 20S after the operation is carried out for 4-8 min and the material is discharged for 60S.
5. The utility model provides a recovery processing system of acid ammonium sulfate waste liquid, its includes the preliminary treatment cauldron, the triple effect evaporimeter, crystallizer, centrifuge and the desiccator that connect in order, its characterized in that: the pretreatment kettle is connected with an acidic ammonium sulfate waste liquid pipeline, an alkali liquid pipeline and a remover pipeline respectively, and is also communicated with the triple-effect evaporator through a material washing branch pipeline, and a cyclone separator is arranged between the triple-effect evaporator and the crystallizer.
6. The system for recovering and treating the waste acidic ammonium sulfate solution as claimed in claim 5, wherein: the triple-effect evaporator is connected with a water flushing pipeline.
7. The system for recovering and treating the waste acidic ammonium sulfate solution as claimed in claim 5, wherein: the crystallizer is provided with a stirrer, a guide cylinder is sleeved on the stirrer, and baffling baffles are arranged on the crystallizer on two sides of the stirrer; and a gap is formed between the baffling baffle and the inner wall of the crystallizer.
8. The system for recovering and treating the waste liquid of acidic ammonium sulfate as claimed in claim 6, wherein: the water flushing pipeline is communicated with the first-effect separator in the three-effect evaporator through a first flushing pipeline, is communicated with the second-effect separator in the three-effect evaporator through a second flushing pipeline, and is communicated with the third-effect separator in the three-effect evaporator through a third flushing pipeline; the material flushing branch pipeline is communicated with the first flushing pipeline.
9. The system for recovering and treating the waste acidic ammonium sulfate solution as claimed in claim 8, wherein: the two-effect separator and the three-effect separator are respectively communicated with the crystallizer through the cyclone separator; the two-effect separator and the three-effect separator also form a loop with the cyclone separator respectively.
10. The system for recovering and treating the waste acidic ammonium sulfate solution as claimed in claim 5, wherein: the centrifuge is communicated with the triple-effect evaporator through a temporary storage tank.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211575729.2A CN115818882A (en) | 2022-12-09 | 2022-12-09 | Method and system for recycling acidic ammonium sulfate waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116639708A (en) * | 2023-06-13 | 2023-08-25 | 山东大成生物化工有限公司 | Method and device for recycling ammonium sulfate from fosetyl-aluminum production waste liquid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116639708A (en) * | 2023-06-13 | 2023-08-25 | 山东大成生物化工有限公司 | Method and device for recycling ammonium sulfate from fosetyl-aluminum production waste liquid |
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