CN216073332U - Industrial waste acid comprehensive treatment system - Google Patents
Industrial waste acid comprehensive treatment system Download PDFInfo
- Publication number
- CN216073332U CN216073332U CN202120625093.2U CN202120625093U CN216073332U CN 216073332 U CN216073332 U CN 216073332U CN 202120625093 U CN202120625093 U CN 202120625093U CN 216073332 U CN216073332 U CN 216073332U
- Authority
- CN
- China
- Prior art keywords
- waste acid
- acid
- tank
- hydrochloric acid
- hydrogen sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002253 acid Substances 0.000 title claims abstract description 143
- 239000002440 industrial waste Substances 0.000 title claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 158
- 239000002699 waste material Substances 0.000 claims abstract description 122
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 36
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 51
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 238000004062 sedimentation Methods 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 32
- 238000005188 flotation Methods 0.000 claims description 30
- 239000010802 sludge Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 17
- 230000008020 evaporation Effects 0.000 claims description 15
- 238000001953 recrystallisation Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000005374 membrane filtration Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- -1 hydrogen ions Chemical class 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 6
- 239000003337 fertilizer Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229960002089 ferrous chloride Drugs 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010805 inorganic waste Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The utility model provides an industrial waste acid comprehensive treatment system, which comprises a waste acid pretreatment unit, an advanced treatment unit, a hydrochloric acid recovery unit and an inorganic salt recovery unit which are sequentially arranged according to process steps, wherein the waste acid pretreatment unit comprises a hydrochloric acid waste acid pretreatment unit and a sulfuric acid waste acid pretreatment unit which are arranged in parallel, the technical problem of large-scale hydrochloric acid volatilization loss in the pretreatment process caused by large-scale ion exchange after mixing of hydrochloric acid waste acid and sulfuric acid waste acid is avoided by independently removing heavy metal elements and insoluble solid impurities in the waste acid, the pretreated hydrochloric acid waste acid and sulfuric acid waste acid are compatible through a compatibility pool, effective components in a compatible liquid are converted into sulfate and hydrochloric acid through the hydrochloric acid recovery unit and the inorganic salt recovery unit, the mass concentration of the obtained hydrochloric acid is more than 20 percent and can be directly used for industrial production, the sulfate can be directly used for compound agricultural fertilizer, and zero emission and resource utilization of sulfuric acid waste acid and hydrochloric acid waste acid are realized.
Description
Technical Field
The utility model belongs to the field of wastewater treatment, and particularly relates to an industrial waste acid comprehensive treatment system.
Background
The industrial waste acid is acid-containing waste liquid which can not be reused in industrial production, the total amount of the waste acid in China is more than two hundred million tons, wherein the inorganic waste acid accounts for about 65 percent, and according to research, the inorganic waste acid in China has the following characteristics: (1) the compositions of waste acid in each industry are similar, but the waste acid generated in each industry is different; (2) the source of the waste acid is wide, the waste acid is dispersed in the industry, the total amount of the waste acid is large, but the amount of the waste acid generated by a single enterprise is small; (3) the waste acid has low concentration, can not be utilized, has strong volatility and high impurity content of heavy metal, toxic organic matters and the like, and can cause irreversible environmental pollution when being discharged.
Typical inorganic waste acid includes hydrochloric acid waste acid and sulfuric acid waste acid, and the existing treatment processes for the hydrochloric acid waste acid and the sulfuric acid waste acid generally include a neutralization method, an extraction method, a roasting method, a displacement method and an evaporation method: the neutralization method is simple and is accepted by most enterprises for individual treatment, but the method has the defects of large medicament consumption, incapability of directly discharging hazardous waste generated by neutralization treatment and high treatment cost; the roasting method is usually used for treating waste hydrochloric acid, the waste acid needs to be oxidized and concentrated in equipment at about 600 ℃, the concentration of regenerated hydrochloric acid can reach more than 20 percent, but the harsh production conditions require the equipment to be resistant to corrosion and high temperature, and the energy consumption of the whole process is higher; the displacement method generally comprises the steps of adding concentrated sulfuric acid into waste hydrochloric acid to obtain concentrated hydrochloric acid and ferrous sulfate products, wherein a large amount of concentrated sulfuric acid is required to be added during the reaction, and the requirement on the corrosion resistance of equipment is high; the evaporation method is mainly used for the evaporation rectification purification of the waste hydrochloric acid, the byproduct of evaporation crystallization is the hydrate of ferric chloride, further treatment and purification are needed, and the method has limited increase of the concentration of the regenerated hydrochloric acid under the condition of not adding an auxiliary agent. It can be seen that the existing treatment processes all have the defects of large medicament investment, higher requirements on the performance of equipment and the utilization of the treated substances after treatment.
SUMMERY OF THE UTILITY MODEL
The embodiment of the utility model provides an industrial waste acid comprehensive treatment system, aiming at comprehensively treating two types of waste water by combining the composition characteristics of hydrochloric acid waste acid and sulfuric acid waste acid, and realizing crystal transformation combination and resource recovery of effective components in the waste acid without adding a large amount of medicaments.
In order to achieve the purpose, the utility model adopts the technical scheme that:
an industrial waste acid comprehensive treatment system comprises a waste acid pretreatment unit, an advanced treatment unit, a hydrochloric acid recovery unit and an inorganic salt recovery unit which are sequentially arranged according to the process steps;
the waste acid pretreatment unit comprises a hydrochloric acid waste acid pretreatment unit and a sulfuric acid waste acid pretreatment unit which are arranged in parallel, and waste acid compatibility pools which are respectively communicated with the liquid outlet pipes of the hydrochloric acid waste acid pretreatment unit and the sulfuric acid waste acid pretreatment unit; the hydrochloric acid waste acid pretreatment unit comprises a first heavy metal sedimentation tank, a first hydrogen sulfide floatation tank and a tail gas absorption device communicated with the first hydrogen sulfide floatation tank; the sulfuric acid waste acid pretreatment unit comprises a second metal sedimentation tank and a second hydrogen disulfide floatation tank, and the second hydrogen disulfide floatation tank is communicated with the tail gas absorption device; the waste acid compatibility pool is used for mixing hydrochloric acid waste acid pretreatment liquid and sulfuric acid waste acid pretreatment liquid and adjusting the concentration of hydrogen ions and chloride ions;
the advanced treatment unit comprises an organic matter adsorption unit and a membrane filtration device which are sequentially communicated with the waste acid compatibility pool;
the hydrochloric acid recovery unit comprises an evaporative crystallizer and a hydrochloric acid condenser connected with a steam outlet end of the evaporative crystallizer;
the inorganic salt recovery unit comprises a recrystallization evaporator connected with the liquid outlet end of the evaporative crystallizer.
In one embodiment, the organic matter adsorption unit comprises an activated carbon adsorber and an activated carbon regenerator, wherein the activated carbon adsorber is connected with the liquid outflow end of the waste acid compatibility pool through a pipeline and is used for adsorbing organic matters in a compatibility liquid; the activated carbon regenerator is used for regenerating activated carbon saturated in adsorption;
the activated carbon adsorber and the activated carbon regenerator are connected through a material transferring pump and used for mutual transfer of activated carbon.
In one embodiment, the evaporative crystallizer is connected with the water production end of the membrane filtration device through a feed pump; the hydrochloric acid condenser is connected with the acid-containing steam of the evaporation crystallizer and is used for condensing water vapor and recovering hydrogen chloride gas.
In one embodiment, the inorganic salt recovery unit further comprises a second solid-liquid separation device and a dryer connected in series with the recrystallization evaporator.
In one embodiment, a crude purification unit is further included between the evaporative crystallizer and the recrystallization evaporator, the crude purification unit including:
the first solid-liquid separation device is connected with a liquid outlet end of the evaporative crystallizer and is used for purifying inorganic salt obtained in the evaporative crystallizer;
the redissolution barrel is used for dissolving the inorganic salt obtained by the separation of the first solid-liquid separation device;
wherein, recrystallization evaporimeter with the solution exit end of redissolving the bucket is connected for recrystallize the inorganic salt aqueous solution of redissolving the bucket, further promote the inorganic salt quality.
In one embodiment, the supernatant of the first heavy metal sedimentation tank overflows to the first hydrogen sulfide flotation tank, the first hydrogen sulfide flotation tank is provided with a first inflation pipeline for introducing hydrogen sulfide gas, and the tail gas absorption device for recovering hydrogen sulfide waste gas is arranged above the first hydrogen sulfide flotation tank;
and the supernatant of the second heavy metal sedimentation tank overflows to the second hydrogen sulfide air flotation tank, the second hydrogen sulfide air flotation tank is provided with a second gas filling pipeline for introducing hydrogen sulfide gas, and a gas collecting hood is arranged above the second hydrogen sulfide air flotation tank and communicated with the tail gas absorption device.
In one embodiment, the bottom of the first heavy metal sedimentation tank and the bottom of the second heavy metal sedimentation tank are provided with sludge scraping devices for collecting and discharging sludge at the bottom of the sedimentation tanks; and the first hydrogen sulfide floatation tank and the second hydrogen sulfide floatation tank are both provided with suspended matter scrapers with adjustable heights, and the suspended matter scrapers are used for collecting and discharging solid suspended matters obtained on the liquid surface after floatation.
In one embodiment, the waste acid pretreatment unit is further provided with a sludge storage tank, and the sludge storage tank is provided with a sludge inlet which is respectively connected with the first heavy metal sedimentation tank, the second heavy metal sedimentation tank, the first hydrogen sulfide flotation tank, the second hydrogen sulfide flotation tank and the membrane filtering device and is used for collecting solid matters obtained in each area in the treatment process.
In one embodiment, the waste acid pretreatment unit is further provided with a filter press connected with a sludge outlet of the sludge storage tank, the filter press is used for separating a solid-liquid mixture in the sludge storage tank, the waste acid pretreatment unit is provided with a sludge inlet, a solid outlet and a liquid outlet, and the liquid outlet is connected with the waste acid compatibility tank and is used for inputting the separated liquid into the system again for treatment.
Illustratively, the first solid-liquid separation device and the second solid-liquid separation device employ centrifuges.
Illustratively, the dryer is a blade dryer, a spray dryer, or a fluidized bed dryer.
The utility model provides an industrialized waste acid comprehensive treatment system, which has the beneficial effects that: the industrial waste acid comprehensive treatment system provided by the embodiment of the utility model is provided with the independent hydrochloric acid waste acid pretreatment unit and the sulfuric acid waste acid pretreatment unit, while respectively removing heavy metal elements and insoluble solid impurities in the waste acid, the technical problem of volatilization loss of a large amount of hydrochloric acid in the pretreatment process due to a large amount of ion exchange generated after the hydrochloric acid waste acid and the sulfuric acid waste acid are mixed is solved, mixing the pretreated hydrochloric acid waste acid and sulfuric acid waste acid by a waste acid compatibility pool, adjusting the ion concentration in the acid solution, then the effective components in the compatible liquid are converted into sulfate and hydrochloric acid by a hydrochloric acid recovery unit and an inorganic salt recovery unit, the mass concentration of the obtained hydrochloric acid is more than 20 percent, the hydrochloric acid can be directly used for industrial production without further purification, the sulfate can be directly used for the production of the compound fertilizer, and the zero emission and resource utilization of the sulfuric acid waste acid and the hydrochloric acid waste acid are really realized.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly describe the embodiments or drawings required in the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic diagram of a processing system according to an embodiment of the present invention;
wherein, in the figures, the respective reference numerals:
10-a waste acid pretreatment unit, 20-a deep treatment unit; 30-hydrochloric acid recovery unit, and 40-inorganic salt recovery unit.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the utility model and are not intended to limit the utility model.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Referring to fig. 1, a system for comprehensive treatment of industrial waste acid according to the present invention will now be described. The industrial waste acid comprehensive treatment system in this embodiment includes a waste acid pretreatment unit 10, an advanced treatment unit 20, a hydrochloric acid recovery unit 30, and an inorganic salt recovery unit 40, which are sequentially arranged according to process steps;
in this embodiment, the waste acid pretreatment unit 10 includes a hydrochloric acid type waste acid pretreatment unit and a sulfuric acid type waste acid pretreatment unit which are arranged in parallel, and a waste acid compatibility pool which is respectively communicated with the liquid outlet pipes of the hydrochloric acid type waste acid pretreatment unit and the sulfuric acid type waste acid pretreatment unit. The hydrochloric acid waste acid pretreatment unit comprises a first heavy metal sedimentation tank, a first hydrogen sulfide floatation tank and a tail gas absorption device communicated with the first hydrogen sulfide floatation tank. The sulfuric acid pretreatment waste acid treatment unit comprises a second heavy metal sedimentation tank and a second hydrogen disulfide floatation tank, and the second hydrogen disulfide floatation tank is communicated with the tail gas absorption device; the waste acid compatibility pool is used for mixing hydrochloric acid waste acid pretreatment liquid and sulfuric acid waste acid pretreatment liquid and adjusting the concentration of hydrogen ions and chloride ions. The advanced treatment unit 20 comprises an organic matter adsorption unit and a membrane filtration device which are sequentially communicated with the waste acid compatibility tank. The hydrochloric acid recovery unit 30 comprises an evaporative crystallizer and a hydrochloric acid condenser connected with a steam outlet end of the evaporative crystallizer; the inorganic salt recovery unit 40 includes a recrystallization evaporator connected to a liquid outlet end of the evaporative crystallizer.
According to the technical scheme, the hydrochloric acid waste acid is led into the first heavy metal sedimentation tank, a small amount of vulcanizing agent is added, the sedimentation of heavy metal ions in the waste acid liquid is realized, the supernatant in the first heavy metal sedimentation tank is transferred to the first hydrogen sulfide air floatation tank, the grease and the small insoluble substances which are not completely settled in the waste acid liquid are floated to the liquid surface to be removed by introducing hydrogen sulfide gas into the first hydrogen sulfide air floatation tank by utilizing the air floatation principle, and the waste gas generated by air floatation enters the tail gas absorption device to be absorbed. The treatment process of the sulfuric acid waste acid in the second heavy metal sedimentation tank and the second hydrogen disulfide floatation tank is the same as the treatment process. Mixing the pretreated hydrochloric acid waste acid and sulfuric acid waste acid according to a certain proportion of ion concentration, adding a certain amount of ferrous chloride and concentrated sulfuric acid, and regulating H in the compatible solution without introducing impurity ions+And Cl-The concentration is close to and more than 6mol/L, organic matters and solid insoluble matters are further removed from the compatible liquid after compatibility through an advanced treatment unit, evaporation is carried out in the evaporation crystallizer, the obtained steam is condensed into high-concentration hydrochloric acid in the hydrochloric acid condenser, the residual substances in the evaporation crystallizer are treated through the recrystallization evaporator, and the inorganic mixed salt of zinc sulfate and ferrous sulfate can be obtained after the quality is further improved.
The utility model provides an industrialized waste acid comprehensive treatment system, which has the beneficial effects that: the industrial waste acid comprehensive treatment system provided by the embodiment of the utility model is provided with the independent hydrochloric acid waste acid pretreatment unit and the sulfuric acid waste acid pretreatment unit, while respectively removing heavy metal elements and insoluble solid impurities in the waste acid, the technical problem of volatilization loss of a large amount of hydrochloric acid in the pretreatment process due to a large amount of ion exchange generated after the hydrochloric acid waste acid and the sulfuric acid waste acid are mixed is solved, mixing the pretreated hydrochloric acid waste acid and sulfuric acid waste acid by a compatibility pool, adjusting the ion concentration in the acid solution, then the effective components in the compatible liquid are converted into sulfate and hydrochloric acid by a hydrochloric acid recovery unit and an inorganic salt recovery unit, the mass concentration of the obtained hydrochloric acid is more than 20 percent, the hydrochloric acid can be directly used for industrial production without further purification, the sulfate can be directly used for the production of the compound fertilizer, and the zero emission and resource utilization of the sulfuric acid waste acid and the hydrochloric acid waste acid are really realized.
The organic substance adsorption unit may be a combination of various devices, and as an embodiment, it includes an activated carbon adsorber and an activated carbon regenerator, the activated carbon adsorber is used to adsorb the organic substances in the compatible liquid, and it may also use a common adsorption device, such as a resin adsorption tower. The activated carbon regenerator is used for regenerating activated carbon saturated in adsorption, and can be changed according to adsorption media.
The evaporation crystallizer is connected with the water production end of the membrane filtering device through a feed pump; the hydrochloric acid condenser is connected with the acid-containing steam of the evaporation crystallizer and is used for condensing water vapor and recovering hydrogen chloride gas.
In this embodiment, in order to obtain an inorganic salt mixture having a high purity and directly usable for agricultural fertilizer components, the inorganic salt recovery unit further includes a second solid-liquid separation device and a dryer connected in series to the recrystallization evaporator.
As a modified embodiment, a crude purification unit is further included between the evaporation crystallizer and the recrystallization evaporator, and the crude purification unit includes: the first solid-liquid separation device is connected with a liquid outlet end of the evaporative crystallizer and is used for purifying inorganic salt obtained in the evaporative crystallizer; the re-dissolving barrel is used for dissolving the inorganic salt obtained by the separation of the first solid-liquid separation device; wherein, recrystallization evaporation with the solution exit end of redissolving the bucket is connected for recrystallize the inorganic salt aqueous solution of redissolving the bucket, further promote the inorganic salt quality.
In this embodiment, the supernatant of the first heavy metal sedimentation tank overflows to the first hydrogen sulfide flotation tank, the first hydrogen sulfide flotation tank is provided with a first inflation pipeline for introducing hydrogen sulfide gas, and the tail gas absorption device for recovering hydrogen sulfide waste gas is arranged above the first hydrogen sulfide flotation tank; and the supernatant of the second heavy metal sedimentation tank overflows to the second hydrogen sulfide air flotation tank, the second hydrogen sulfide air flotation tank is provided with a second gas filling pipeline for introducing hydrogen sulfide gas, and a gas collecting hood is arranged above the second hydrogen sulfide air flotation tank and communicated with the tail gas absorption device.
As an improved embodiment, in order to facilitate the collection of solid pollutants generated in the treatment process, the bottom of the first heavy metal sedimentation tank and the bottom of the second heavy metal sedimentation tank are provided with sludge scraping devices for collecting and discharging sludge at the bottom of the sedimentation tanks; and the first hydrogen sulfide air flotation tank and the second hydrogen sulfide air flotation tank are provided with suspended matter collecting devices with adjustable heights and used for collecting and discharging solid suspended matters obtained on the liquid surface after air flotation.
In one embodiment, in order to collect solid pollutants generated in the treatment process and avoid direct discharge of the solid pollutants to pollute the environment, the waste acid pretreatment unit is further provided with a sludge storage tank, and the sludge storage tank is provided with a sludge inlet which is respectively connected with the first heavy metal sedimentation tank, the second heavy metal sedimentation tank, the first hydrogen sulfide air flotation tank, the second hydrogen sulfide air flotation tank and the membrane filtration device and is used for collecting solid matters obtained in each area in the treatment process.
In one embodiment, in order to further recover the waste liquid in the sludge storage tank, the system further comprises a filter press connected with the outlet of the sludge storage tank, the filter press is used for separating the solid-liquid mixture in the sludge storage tank, and is provided with a sludge inlet, a solid outlet and a liquid outlet, and the liquid outlet is connected with the waste acid compatibility tank and is used for inputting the separated liquid into the system again for treatment.
In this embodiment, the first solid-liquid separation device and the second solid-liquid separation device employ centrifuges.
In this embodiment, the drying device is a scraper dryer, a spray dryer, or a fluidized bed dryer.
In summary, the following describes the operation flow of the present application with a specific embodiment:
leading 0.5t of hydrochloric acid waste acid into a first heavy metal sedimentation tank, wherein the hydrochloric acid waste acid contains 10 percent of zinc chlorideAdding 25% ferrous chloride and 5% hydrochloric acid into a first heavy metal sedimentation tank, reacting for 10min after adding 0.05kg of vulcanizing agent, after precipitating for 30min, collecting the precipitate at the bottom of the first heavy metal sedimentation tank by using a mud scraper, transferring the precipitate to a mud storage tank, overflowing the clear liquid at the top to a first hydrogen sulfide air flotation tank, adjusting the outlet of a first inflation pipeline to be 5m away from the liquid level, introducing hydrogen sulfide gas for air flotation, wherein the gas-liquid ratio of the gas consumption for air flotation to the acid liquid in the tank is 0.1m3Collecting suspended substances obtained by air floatation through a suspended substance scraper and transferring the suspended substances to a sludge storage tank, wherein waste gas generated by air floatation flows into a tail gas absorption device; 0.5t of sulfuric acid waste acid is led into a second heavy metal sedimentation tank, the sulfuric acid waste water contains 25 percent of ferrous sulfate and 25 percent of sulfuric acid, and the treatment process is the same as that of hydrochloric acid waste acid.
The two kinds of waste water after treatment are compatible in a waste acid compatibility pool, 0.25t of concentrated sulfuric acid with the concentration of 98 percent and 0.3t of ferrous chloride are added to adjust the concentration of H + and Cl-in the compatible liquid to be similar to and more than 6mol/L, the compatible liquid is treated by an activated carbon adsorber to remove organic matters in the waste acid, the TOC in the treated compatible liquid is less than 30mg/L, the treated compatible liquid is filtered by a membrane filter device to remove micro insoluble substances and activated carbon particles and then enters an evaporation crystallizer to be evaporated, finally 1.05t of hydrochloric acid with the mass concentration of 20 percent is obtained in a hydrochloric acid condenser and can be directly used for industrial production, inorganic crude salt mixture obtained by the evaporation crystallizer is separated by a first centrifugal machine, the obtained crude salt is re-dissolved in a re-dissolving bucket and then is led into the re-crystallizing evaporation device, the solid obtained by re-crystallization is purified by a second centrifugal machine and a drying machine to obtain 0.5t of mixture of zinc sulfate and ferrous sulfate, can be directly used for producing compound agricultural fertilizer.
And (4) revenue accounting: the market selling price of the ferrous sulfate and the zinc sulfate is larger than 2000 yuan/ton independently, the market selling price of 31 percent concentrated hydrochloric acid is 450 yuan/ton according to the minimum value, an enterprise uses hydrochloric acid to dilute the hydrochloric acid to 20 percent for use, and the economic benefit of comprehensively calculating the resource by-products is about 1300 yuan.
Cost: the comprehensive operation cost of the heavy metal sedimentation tank, the hydrogen sulfide floatation tank, the activated carbon adsorber and the membrane filtering device of the system is 5-10 yuan, the price of commercially available high ferrous chloride is different from 1500-. The comprehensive operation cost of the evaporation crystallizer, the hydrochloric acid condenser and the dryer is 150-180 Yuan/ton of waste acid treatment capacity, and the operation cost of the recrystallization evaporator is 120-160 Yuan/ton of crude salt.
The economic benefits of 0.5t hydrochloric acid waste acid and 0.5t sulfuric acid waste acid are comprehensively calculated to be more than 300 yuan, the price of a consumable product is calculated to be a high value, the price of a produced product is calculated to be a low value, and the overall calculation is conservative. According to the situation of North China, if the delivery treatment cost (not counting the transportation cost) of 400-one acid/ton of the waste acid is 600 yuan/ton, the comprehensive benefit of the whole process is higher than 700 yuan/ton treatment capacity, and the recovery and resource utilization of the effective components in the sulfuric acid waste acid and the hydrochloric acid waste acid are realized while the hydrochloric acid waste acid and the sulfuric acid waste acid are comprehensively treated.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the utility model, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. An industrial waste acid comprehensive treatment system is characterized by comprising a waste acid pretreatment unit, an advanced treatment unit, a hydrochloric acid recovery unit and an inorganic salt recovery unit which are sequentially arranged according to process steps;
the waste acid pretreatment unit comprises a hydrochloric acid waste acid pretreatment unit and a sulfuric acid waste acid pretreatment unit which are arranged in parallel, and waste acid compatibility pools which are respectively communicated with the liquid outlet pipes of the hydrochloric acid waste acid pretreatment unit and the sulfuric acid waste acid pretreatment unit; the hydrochloric acid waste acid pretreatment unit comprises a first heavy metal sedimentation tank, a first hydrogen sulfide floatation tank and a tail gas absorption device communicated with the first hydrogen sulfide floatation tank; the sulfuric acid pretreatment waste acid treatment unit comprises a second heavy metal sedimentation tank and a second hydrogen disulfide floatation tank, and the second hydrogen disulfide floatation tank is communicated with the tail gas absorption device; the waste acid compatibility pool is used for mixing hydrochloric acid waste acid pretreatment liquid and sulfuric acid waste acid pretreatment liquid and adjusting the concentration of hydrogen ions and chloride ions;
the advanced treatment unit comprises an organic matter adsorption unit and a membrane filtration device which are sequentially communicated with the waste acid compatibility pool;
the hydrochloric acid recovery unit comprises an evaporative crystallizer and a hydrochloric acid condenser connected with a steam outlet end of the evaporative crystallizer;
the inorganic salt recovery unit comprises a recrystallization evaporator connected with the liquid outlet end of the evaporative crystallizer.
2. The comprehensive treatment system for industrial waste acid as claimed in claim 1, wherein the organic substance adsorption unit comprises an activated carbon adsorber and an activated carbon regenerator, and the activated carbon adsorber is connected to the liquid outflow end of the waste acid compatibility tank through a pipeline and is used for adsorbing organic substances in a compatible liquid; the activated carbon regenerator is used for regenerating activated carbon with saturated adsorption.
3. The comprehensive industrial waste acid treatment system as claimed in claim 1, wherein said evaporative crystallizer is connected to the water production end of said membrane filtration unit by a feed pump;
the hydrochloric acid condenser is connected with the acid-containing steam of the evaporation crystallizer and is used for condensing water vapor and recovering hydrogen chloride gas.
4. The integrated industrial waste acid treatment system according to claim 1, wherein said inorganic salt recovery unit further comprises a second solid-liquid separation device and a dryer connected in series to said recrystallization evaporator.
5. The comprehensive industrial waste acid treatment system according to claim 4, further comprising a crude purification unit between said evaporative crystallizer and said recrystallization evaporator, said crude purification unit comprising:
the first solid-liquid separation device is connected with a liquid outlet end of the evaporative crystallizer and is used for purifying inorganic salt obtained in the evaporative crystallizer;
the redissolution barrel is used for dissolving the inorganic salt obtained by the separation of the first solid-liquid separation device;
wherein, recrystallization evaporimeter with the solution exit end of redissolving the bucket is connected for recrystallize the inorganic salt aqueous solution of redissolving the bucket, further promote the inorganic salt quality.
6. The comprehensive treatment system for industrial waste acid as claimed in claim 1, wherein the supernatant of the first heavy metal sedimentation tank overflows to the first hydrogen sulfide flotation tank, the first hydrogen sulfide flotation tank is provided with a first inflation pipeline for introducing hydrogen sulfide gas, and the tail gas absorption device for recovering hydrogen sulfide waste gas is arranged above the first hydrogen sulfide flotation tank;
and the supernatant of the second heavy metal sedimentation tank overflows to the second hydrogen sulfide air flotation tank, the second hydrogen sulfide air flotation tank is provided with a second gas filling pipeline for introducing hydrogen sulfide gas, and a gas collecting hood is arranged above the second hydrogen sulfide air flotation tank and communicated with the tail gas absorption device.
7. The comprehensive treatment system for industrial waste acid as claimed in claim 6, wherein the bottom of the first heavy metal sedimentation tank and the bottom of the second heavy metal sedimentation tank are provided with mud scraping devices for collecting and discharging the sludge at the bottom of the sedimentation tanks; and/or
And the first hydrogen sulfide floatation tank and the second hydrogen sulfide floatation tank are provided with suspended matter scrapers with adjustable heights, and the suspended matter scrapers are used for collecting and discharging solid suspended matters obtained on the liquid surface after floatation.
8. The comprehensive treatment system for industrial waste acid as claimed in claim 6, wherein the waste acid pretreatment unit is further provided with a sludge storage tank, and the sludge storage tank is provided with a sludge inlet respectively connected with the first heavy metal sedimentation tank, the second heavy metal sedimentation tank, the first hydrogen sulfide flotation tank, the second hydrogen sulfide flotation tank and the membrane filtration device.
9. The industrial waste acid integrated treatment system of claim 5, wherein the first solid-liquid separation device and the second solid-liquid separation device employ centrifuges.
10. The industrial waste acid integrated processing system of claim 4, wherein the dryer is a drag dryer, a spray dryer, or a fluidized bed dryer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202120625093.2U CN216073332U (en) | 2021-03-26 | 2021-03-26 | Industrial waste acid comprehensive treatment system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202120625093.2U CN216073332U (en) | 2021-03-26 | 2021-03-26 | Industrial waste acid comprehensive treatment system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN216073332U true CN216073332U (en) | 2022-03-18 |
Family
ID=80634947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202120625093.2U Active CN216073332U (en) | 2021-03-26 | 2021-03-26 | Industrial waste acid comprehensive treatment system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN216073332U (en) |
-
2021
- 2021-03-26 CN CN202120625093.2U patent/CN216073332U/en active Active
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101555053B (en) | A composite coagulant and treatment method that can be used to treat rare earth high-concentration ammonia nitrogen wastewater and recover industrial-grade ammonium chloride | |
| CN105540973B (en) | High arsenic acid water purification and the method recycled | |
| CN102079601B (en) | Resource recovery and zero discharge process for treating rare-earth wet-method smelting wastewater | |
| CN105480988B (en) | A kind of method that high-purity ammonium salt is prepared from impurity ammonium salt waste liquid high | |
| CN102936070A (en) | Method for treating mercury-containing wastewater during PVC (Polyvinyle Chloride) production through two-step process | |
| CN102010082A (en) | Treatment method for recycling waste dilute sulfuric acid | |
| CN113292187A (en) | Resourceful treatment method and device for high-concentration ammonia nitrogen wastewater | |
| CN102126917B (en) | High purity recycling and energy integration technology for different concentrations of dichloromethane wastewater | |
| CN112759162B (en) | Method and system for recycling waste acid | |
| CN112679025B (en) | A treatment system and method for reducing and solidifying the leachate of electrolytic aluminum slag and recycling its resources | |
| CN214141986U (en) | Processing system for reducing and solidifying resource recycling of electrolytic aluminum slag leachate | |
| CN111039492A (en) | Low-cost zero-discharge desulfurization wastewater treatment system and method | |
| CN110683698A (en) | Wet smelting wastewater zero-discharge recycling production process | |
| CN104229757B (en) | A kind of method of dirty acid purification being processed to Returning process recycling | |
| CN216073332U (en) | Industrial waste acid comprehensive treatment system | |
| CN207862094U (en) | A kind of electroplating waste-water reutilizing and the processing system of zero-emission | |
| CN108911343A (en) | Polysilicon zero emission method of wastewater and system | |
| CN110818158A (en) | Comprehensive treatment method for waste hydrochloric acid and sludge containing heavy metals | |
| CN204874165U (en) | System for salt content in reduction desulfurization waste liquid | |
| CN209143930U (en) | A kind of coal fired power plant desulfurization wastewater dechlorination processing unit | |
| CN207986914U (en) | A kind of washes zero-discharge treatment system | |
| CN207904066U (en) | A kind of processing system of the waste water containing sodium nitrate | |
| CN117401841A (en) | High-salt organic wastewater recycling treatment device and method | |
| CN87103664A (en) | Synthetic glass factory cyanide wastewater treatment process method | |
| CN202144469U (en) | Waste acid recovery device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |