CN112028368B - System and method for treating waste hydrochloric acid and waste brine in production of titanium dioxide chloride - Google Patents
System and method for treating waste hydrochloric acid and waste brine in production of titanium dioxide chloride Download PDFInfo
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- CN112028368B CN112028368B CN202010976381.2A CN202010976381A CN112028368B CN 112028368 B CN112028368 B CN 112028368B CN 202010976381 A CN202010976381 A CN 202010976381A CN 112028368 B CN112028368 B CN 112028368B
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- 239000002699 waste material Substances 0.000 title claims abstract description 224
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 192
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 115
- 239000012267 brine Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- NSYYPXSKPGPMBW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].Cl Chemical compound [O-2].[O-2].[Ti+4].Cl NSYYPXSKPGPMBW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000012528 membrane Substances 0.000 claims abstract description 70
- 238000000926 separation method Methods 0.000 claims abstract description 63
- 239000002253 acid Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 230000008020 evaporation Effects 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000000108 ultra-filtration Methods 0.000 claims description 36
- 230000001105 regulatory effect Effects 0.000 claims description 34
- 238000004062 sedimentation Methods 0.000 claims description 25
- 230000001699 photocatalysis Effects 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 230000001112 coagulating effect Effects 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000010306 acid treatment Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 241000894006 Bacteria Species 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 8
- 238000000265 homogenisation Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 16
- 238000004064 recycling Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 7
- 230000007935 neutral effect Effects 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
The invention discloses a system and a method for treating waste hydrochloric acid and waste brine in titanium dioxide chloride production. The method comprises the steps of performing membrane separation and physical and chemical purification treatment on waste hydrochloric acid to remove heavy metal impurities in the waste hydrochloric acid to obtain clean acid; mixing clean acid with waste brine subjected to catalytic reduction and high-concentration sodium hypochlorite removal, and then removing Na in the waste brine 2 CO 3 And alkaline substances such as NaOH, so as to obtain neutral brine; and then, the neutral brine is subjected to deep recycling treatment by adopting the processes of primary membrane separation treatment, MVR evaporation and secondary membrane separation treatment in sequence, so that clean water which can be used for producing recycling and recyclable crystalline salt are obtained, and the recycling of resources is realized.
Description
Technical Field
The invention relates to the technical field of pollutant treatment, in particular to a treatment system and a treatment method for waste hydrochloric acid and waste brine in titanium dioxide chloride production.
Background
The production method of titanium dioxide mainly comprises a sulfuric acid method and a chlorination method, wherein the titanium dioxide produced by the chlorination method has high purity and good quality, but a large amount of chemical agents including hydrochloric acid, sodium hypochlorite and the like are needed in the production process, and intermediate products are separated, purified and purified, so that a large amount of waste liquid is generated in the process.
At present, waste liquid generated in the production process of titanium dioxide chloride mainly comprises waste hydrochloric acid and waste brine, wherein the waste hydrochloric acid contains a small amount of heavy metal ions besides high-concentration hydrochloric acid, and the main component of the waste brine is sodium hypochlorite (NaClO), a plurality of heavy metal ions and Na 2 CO 3 And NaOH, etc. The most commonly used treatment method at the present stage is to directly mix the two waste liquids, and treat the two waste liquids by a waste treatment method. The method has simple process and low running cost, but can generate a large amount of high-concentration chlorine in the mixing process, and can cause serious secondary pollution and even serious personnel poisoning. In addition, the method mixes and reacts two waste liquids, and serious and massive resource waste is caused. Therefore, development of efficient purification technology is required for advanced treatment of such waste liquid.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a treatment system for waste hydrochloric acid and waste brine in the production of titanium dioxide chloride.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the system comprises a waste hydrochloric acid treatment system and a waste brine treatment system, wherein the waste hydrochloric acid treatment system comprises a waste hydrochloric acid ultrafiltration system, a waste acid membrane separation system and a concentrated solution collecting tank which are sequentially connected, and the waste hydrochloric acid ultrafiltration system is connected with the concentrated solution collecting tank through a pipeline; the waste brine treatment system comprises an integrated precipitation system 1, a waste brine regulating tank, an integrated precipitation system 2, a waste brine ultrafiltration system, a photocatalytic oxidation system, a mixing tank, a degassing device, a primary membrane separation system, an MVR evaporation system and a secondary membrane separation system which are sequentially connected, wherein the concentrated solution collecting tank is connected with the integrated precipitation system 1 through a pipeline, the waste brine ultrafiltration system is connected with the waste brine regulating tank through a pipeline, the waste acid membrane separation system is connected with the mixing tank through a pipeline, the primary membrane separation system is connected with the waste brine regulating tank through a pipeline, and the secondary membrane separation system is connected with the waste brine regulating tank through a pipeline.
In the treatment system for the waste hydrochloric acid and the waste brine in the production of the titanium dioxide chloride, the waste hydrochloric acid treatment system can carry out pretreatment of ultrafiltration and membrane concentration on the waste hydrochloric acid, and impurities in the waste hydrochloric acid can be removed to obtain clean acid;
the waste brine treatment system can perform precipitation-ultrafiltration-photocatalysis pretreatment on the waste brine to remove impurities and high-concentration sodium hypochlorite, then mixing and adjusting the waste brine in a mixing tank with clean acid, and obtaining clean water for producing and recycling and recyclable crystalline salt through a process of degassing-primary membrane separation-MVR evaporation-secondary membrane separation.
The waste hydrochloric acid treatment system can efficiently degrade organic matters and simultaneously can efficiently desalt.
Further, the photocatalytic oxidation system comprises a plurality of reaction devices connected in series, a plurality of ultraviolet lamps are arranged in each reaction device, and high-concentration available chlorine in the wastewater is degraded in a photocatalytic mode.
Further, the number of the reaction devices is 8 to 10.
Further, 10-15 ultraviolet lamps are arranged in each reaction device, the power of each ultraviolet lamp is 15-20w, and the effective chlorine in the wastewater is completely degraded into chloride ions through the irradiation of the high-intensity ultraviolet lamps.
Further, the waste hydrochloric acid treatment system further comprises a waste hydrochloric acid regulating tank for carrying out homogenizing regulation treatment on waste hydrochloric acid, and the waste hydrochloric acid regulating tank is connected with the waste hydrochloric acid ultrafiltration system.
The invention also provides a treatment method of the waste hydrochloric acid and the waste brine in the production of the titanium dioxide chloride, which comprises the following steps:
(1) After the waste hydrochloric acid is subjected to homogenization adjustment, particles, colloid, bacteria and organic matters are removed through a waste hydrochloric acid ultrafiltration system, ultrafiltered concentrated water enters a concentrated liquid collecting tank, produced water enters a waste acid membrane separation system for membrane separation, concentrated water treated by the waste acid membrane separation system enters a concentrated water collecting tank, and produced water enters a mixing tank; the heavy metal ions are removed from the concentrated water in the concentrated liquid collecting tank through the integrated precipitation system 1 added with the coagulating sedimentation agent A, and then the concentrated water flows into the waste brine regulating tank;
(2) After the waste brine is subjected to homogenization adjustment, the waste brine enters an integrated precipitation system 2 added with a coagulating sedimentation agent B to remove heavy metal ions and particulate matters, then particles, colloid, bacteria and organic matters are removed through a waste brine ultrafiltration system, concentrated water of the waste brine ultrafiltration system flows back to a waste brine adjusting tank, and produced water enters a photocatalytic oxidation system to degrade available chlorine through photocatalytic reaction;
(3) Mixing produced water of the photocatalytic oxidation system in the step (2) with produced water of the waste hydrochloric acid ultrafiltration system in the step (1), removing alkaline substances through acid-base neutralization, enabling the degassed product water to enter a primary membrane separation system, enabling concentrated water of the primary membrane separation system to flow back to a waste brine regulating tank, enabling produced water to enter an MVR evaporation system for evaporation, enabling evaporated crystal salt to be reused for titanium dioxide production, enabling the concentrated water to enter a secondary membrane separation system, and enabling the concentrated water of the secondary membrane separation system to flow back to the waste brine regulating tank.
The method comprises the steps of performing membrane separation and physical and chemical purification treatment on waste hydrochloric acid to remove heavy metal impurities in the waste hydrochloric acid to obtain clean acid; mixing clean acid with waste brine subjected to photocatalytic degradation and removed with high-concentration sodium hypochlorite, and then removing Na in the waste brine 2 CO 3 And alkaline substances such as NaOH, so as to obtain neutral brine with pH of approximately 7; and then, the neutral brine is subjected to deep recycling treatment through the processes of primary membrane separation treatment, MVR evaporation and secondary membrane separation treatment in sequence, so that clean water which can be used for producing recycling and recyclable crystalline salt are obtained.
According to the invention, the waste hydrochloric acid and the waste brine are respectively and independently pretreated, impurities in the waste hydrochloric acid and the waste brine are removed, and then the waste hydrochloric acid and the waste brine are mixed, and the waste hydrochloric acid and the waste brine are deeply treated, produced and recycled through membrane separation and MVR evaporation.
Further, the coagulating sedimentation agent A comprises alkaline substances, PAC and PAM, so that heavy metal ions in the wastewater are effectively removed.
Further, the coagulating sedimentation agent B comprises PAC and PAM, and heavy metal ions and particulate matters in the wastewater are removed.
Compared with the prior art, the invention has the beneficial effects that:
(1) The system of the invention carries out independent pretreatment on the waste hydrochloric acid and the waste brine respectively, removes pollutants in the waste hydrochloric acid and the waste brine, and then carries out subsequent treatment by mixing and adjusting the waste hydrochloric acid and the waste brine, thereby realizing the neutralization of waste water with extremely strong acidity and alkalinity and avoiding secondary pollution caused by chlorine generated by direct contact of effective chlorine and acid.
(2) The system is a zero emission system, wherein concentrated water treated by each stage of membrane separation system is concentrated and pretreated simply and then used for water quality adjustment, and produced water is subjected to multistage advanced treatment to realize production and recycling. In the whole system, except the generated sludge, no pollutant is discharged, and all waste water and crystalline salt can be recycled for production.
Drawings
Fig. 1 is a schematic structural diagram of a treatment system for waste hydrochloric acid and waste brine in the production of titanium dioxide chloride in example 1.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
The system comprises a waste hydrochloric acid treatment system and a waste brine treatment system, wherein the waste hydrochloric acid treatment system comprises a waste hydrochloric acid ultrafiltration system, a waste acid membrane separation system and a concentrated solution collecting tank which are sequentially connected, and the waste hydrochloric acid ultrafiltration system is connected with the concentrated solution collecting tank through a pipeline; the waste brine treatment system comprises an integrated precipitation system 1, a waste brine regulating tank, an integrated precipitation system 2, a waste brine ultrafiltration system, a photocatalytic oxidation system, a mixing tank, a degassing device, a primary membrane separation system, an MVR evaporation system and a secondary membrane separation system which are sequentially connected, wherein the concentrated solution collecting tank is connected with the integrated precipitation system 1 through a pipeline, the waste brine ultrafiltration system is connected with the waste brine regulating tank through a pipeline, the waste acid membrane separation system is connected with the mixing tank through a pipeline, the primary membrane separation system is connected with the waste brine regulating tank through a pipeline, and the secondary membrane separation system is connected with the waste brine regulating tank through a pipeline.
In the treatment system for the waste hydrochloric acid and the waste brine in the production of the titanium dioxide chloride, the waste hydrochloric acid treatment system can carry out pretreatment of ultrafiltration and membrane concentration on the waste hydrochloric acid, and impurities in the waste hydrochloric acid can be removed to obtain clean acid;
the waste brine treatment system can perform precipitation-ultrafiltration-photocatalysis pretreatment on the waste brine to remove impurities and high-concentration sodium hypochlorite, then mixing and adjusting the waste brine in a mixing tank with clean acid, and obtaining clean water for producing and recycling and recyclable crystalline salt through a process of degassing-primary membrane separation-MVR evaporation-secondary membrane separation.
The waste hydrochloric acid treatment system can efficiently degrade organic matters and simultaneously can efficiently desalt.
In the invention, the photocatalytic oxidation system comprises a plurality of reaction devices connected in series, and each reaction device is internally provided with a plurality of ultraviolet lamps, so that high-concentration available chlorine in the wastewater is degraded in a photocatalytic manner.
In the present invention, the number of reaction devices is 8 to 10.
In the invention, 10-15 ultraviolet lamps are arranged in each reaction device, the power of each ultraviolet lamp is 15-20w, and the effective chlorine in the wastewater is completely degraded into chloride ions through the irradiation of the high-intensity ultraviolet lamps.
In the invention, the waste hydrochloric acid treatment system further comprises a waste hydrochloric acid regulating tank for carrying out homogenizing regulation treatment on waste hydrochloric acid, and the waste hydrochloric acid regulating tank is connected with the waste hydrochloric acid ultrafiltration system.
The degasser selected by the invention comprises a degasser.
A method for treating waste hydrochloric acid and waste brine in the production of titanium dioxide chloride comprises the following steps:
(1) After the waste hydrochloric acid is subjected to homogenization adjustment, particles, colloid, bacteria and organic matters are removed through a waste hydrochloric acid ultrafiltration system, ultrafiltered concentrated water enters a concentrated liquid collecting tank, produced water enters a waste acid membrane separation system for membrane separation, concentrated water treated by the waste acid membrane separation system enters a concentrated water collecting tank, and produced water enters a mixing tank; the heavy metal ions are removed from the concentrated water in the concentrated liquid collecting tank through the integrated precipitation system 1 added with the coagulating sedimentation agent A, and then the concentrated water flows into the waste brine regulating tank;
(2) After the waste brine is subjected to homogenization adjustment, the waste brine enters an integrated precipitation system 2 added with a coagulating sedimentation agent B to remove heavy metal ions and particulate matters, then particles, colloid, bacteria and organic matters are removed through a waste brine ultrafiltration system, concentrated water of the waste brine ultrafiltration system flows back to a waste brine adjusting tank, and produced water enters a photocatalytic oxidation system to degrade available chlorine through photocatalytic reaction;
(3) Mixing produced water of the photocatalytic oxidation system in the step (2) with produced water of the waste hydrochloric acid ultrafiltration system in the step (1), removing alkaline substances through acid-base neutralization, enabling the degassed product water to enter a primary membrane separation system, enabling concentrated water of the primary membrane separation system to flow back to a waste brine regulating tank, enabling produced water to enter an MVR evaporation system for evaporation, enabling evaporated crystal salt to be reused for titanium dioxide production, enabling the concentrated water to enter a secondary membrane separation system, and enabling the concentrated water of the secondary membrane separation system to flow back to the waste brine regulating tank.
The method comprises the steps of performing membrane separation and physical and chemical purification treatment on waste hydrochloric acid to remove heavy metal impurities in the waste hydrochloric acid to obtain clean acid; mixing clean acid with waste brine subjected to catalytic reduction and high-concentration sodium hypochlorite removal, and then removing Na in the waste brine 2 CO 3 And alkaline substances such as NaOH, so as to obtain neutral brine; and then, the neutral brine is subjected to deep recycling treatment through the processes of primary membrane separation treatment, MVR evaporation and secondary membrane separation treatment in sequence, so that clean water which can be used for producing recycling and recyclable crystalline salt are obtained.
According to the invention, the waste hydrochloric acid and the waste brine are respectively and independently pretreated, impurities in the waste hydrochloric acid and the waste brine are removed, and then the waste hydrochloric acid and the waste brine are mixed, and the waste hydrochloric acid and the waste brine are deeply treated, produced and recycled through membrane separation and MVR evaporation.
In the invention, the coagulating sedimentation agent A comprises alkaline substances, PAC and PAM, so that heavy metal ions in the wastewater can be removed more effectively.
In the invention, the coagulating sedimentation agent B comprises PAC and PAM, and heavy metal ions and particulate matters in the wastewater are removed.
In the invention, the adding amount of the coagulating sedimentation agent A and the coagulating sedimentation agent B can be correspondingly adjusted according to actual conditions.
Example 1
The treatment system for producing waste hydrochloric acid and waste brine by using titanium dioxide chloride in the embodiment is shown in fig. 1, and comprises a waste hydrochloric acid treatment system and a waste brine treatment system, wherein the waste hydrochloric acid treatment system comprises a waste hydrochloric acid regulating tank, a waste hydrochloric acid ultrafiltration system, a waste acid membrane separation system and a concentrated solution collecting tank which are sequentially connected, and the waste hydrochloric acid ultrafiltration system is connected with the concentrated solution collecting tank through a pipeline; the waste brine treatment system comprises an integrated sedimentation system 1, a waste brine regulating tank, an integrated sedimentation system 2, a waste brine ultrafiltration system, a photocatalytic oxidation system, a mixing tank, a degassing device, a primary membrane separation system, an MVR evaporation system and a secondary membrane separation system which are sequentially connected, wherein the concentrated solution collecting tank is connected with the integrated sedimentation system 1 through a pipeline, the waste brine ultrafiltration system is connected with the waste brine regulating tank through a pipeline, the waste acid membrane separation system is connected with the mixing tank through a pipeline, the primary membrane separation system is connected with the waste brine regulating tank through a pipeline, and the secondary membrane separation system is connected with the waste brine regulating tank through a pipeline; the photocatalytic oxidation system comprises 10 reaction tanks which are connected in series, 10 ultraviolet lamps are arranged in each reaction tank, and the power of each ultraviolet lamp is 20w.
The treatment method of the waste hydrochloric acid and the waste brine in the production of the titanium dioxide chloride comprises the following steps:
(1) Waste hydrochloric acid (50 t) treatment process
The water quality of the waste hydrochloric acid is as follows: HCl concentration=20-25 wt%, ss=87.3 Mg/L, ti= 22680Mg/L, v=652.2 Mg/L, fe=92.4 Mg/L, si=76.5 Mg/L, al=58.9 Mg/L, mg=28.2 Mg/L, cr=8.23 Mg/L, mn=4.87 Mg/L, ca=44.3 Mg/L.
After the waste hydrochloric acid is subjected to homogenization adjustment in a waste hydrochloric acid adjusting tank, particles, colloid, bacteria and organic matters in the waste hydrochloric acid are removed through a waste hydrochloric acid ultrafiltration system, ultrafiltered concentrated water enters a concentrated liquid collecting tank, produced water enters a subsequent waste acid membrane separating system, produced water (clean acid) treated by the waste acid membrane separating system is recycled to a mixing tank of a waste brine treatment system, and the concentrated water also enters the concentrated liquid collecting tank.
The indexes of the clean acid are as follows:
HCl concentration=20-25%, ti= 312.3mg/L, v=7.05 mg/L, fe=1.18 mg/L, si=2.12 mg/L, al=1.39 mg/L, the remaining components were not detected.
Concentrated water in the concentrated solution collecting tank enters the integrated precipitation system 1, and the coagulating sedimentation agent A comprises alkali liquor, PAC and PAM, so that heavy metal ions in the concentrated solution are removed, and the wastewater with heavy metals removed is used for homogenizing and adjusting the wastewater brine in the wastewater brine adjusting tank.
(2) Treatment process of waste brine (150 t)
The waste brine water quality is as follows: available chlorine=7.5-8%, ss=55.4 mg/L, naoh=1.8%, na 2 CO 3 ＝4.5％，Ti＝904.6mg/L，Fe＝9.2mg/L，Si＝34.6mg/L，Al＝5.62mg/L，Cr＝3.25mg/L，Mn＝2.78mg/L，V＝10.28mg/L，Ca＝4.27mg/L，Mg＝5.43mg/L。
After the waste brine is subjected to homogenization adjustment in a waste brine adjusting tank (the adjusting water is sourced from a concentrated solution collecting tank in a waste hydrochloric acid treatment system), the waste brine enters an integrated precipitation system 2, a coagulating sedimentation agent B is added, the coagulating sedimentation agent B comprises PAC and PAM, heavy metal ions and particulate matters in the coagulating sedimentation agent B are removed, then the heavy metal ions and particulate matters are removed through a waste hydrochloric acid ultrafiltration system, particles, colloid, bacteria and organic matters in the coagulating sedimentation agent B are removed, concentrated water generated by ultrafiltration flows back to the waste brine adjusting tank, produced water enters a photocatalytic oxidation system, the photocatalytic oxidation system degrades high-concentration available chlorine in waste water in a photocatalytic manner, the photocatalytic oxidation system is formed by connecting 8 reaction tanks in series, 10 ultraviolet lamps are arranged in each reaction tank, the power of each ultraviolet lamp is 20w, and the system can completely degrade available chlorine into chloride ions through irradiation of the high-intensity ultraviolet lamps.
The produced water treated by the system is mixed with clean acid separated by a waste hydrochloric acid treatment system membrane in a mixing tank, and Na in the wastewater is removed by neutralization of acid and alkali 2 CO 3 And alkaline substances such as NaOH. Due to the high concentration of CO generated after the reaction 2 Therefore, the wastewater needs to be CO removed by a degasser 2 . CO removal 2 The waste water after entering the first-stage membrane separation system, the concentrated water after being treated by the first-stage membrane separation system flows back to the waste brine regulating tank, the produced water enters the MVR evaporation system for evaporation, the crystallized salt obtained after evaporation is reused for titanium dioxide production, the condensate enters the second-stage membrane separation system, the concentrated water after being treated by the second-stage membrane separation system flows back to the waste brine regulating tank, and the produced water is reused for production.
The water quality of the produced water is as follows: ph=7.81, ss=1.54 mg/L, fe=0.087 mg/L, substantially meeting the reuse standard.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. The treatment system is characterized by comprising a waste hydrochloric acid treatment system and a waste brine treatment system, wherein the waste hydrochloric acid treatment system comprises a waste hydrochloric acid ultrafiltration system, a waste acid membrane separation system and a concentrated solution collecting tank which are sequentially connected, and the waste hydrochloric acid ultrafiltration system is connected with the concentrated solution collecting tank through a pipeline; the waste brine treatment system comprises an integrated sedimentation system 1, a waste brine regulating tank, an integrated sedimentation system 2, a waste brine ultrafiltration system, a photocatalytic oxidation system, a mixing tank, a degassing device, a primary membrane separation system, an MVR evaporation system and a secondary membrane separation system which are sequentially connected, wherein the concentrated solution collecting tank is connected with the integrated sedimentation system 1 through a pipeline, the waste brine ultrafiltration system is connected with the waste brine regulating tank through a pipeline, the waste acid membrane separation system is connected with the mixing tank through a pipeline, the primary membrane separation system is connected with the waste brine regulating tank through a pipeline, and the secondary membrane separation system is connected with the waste brine regulating tank through a pipeline;
the treatment method of the waste hydrochloric acid and the waste brine in the production of the titanium dioxide chloride based on the treatment system comprises the following steps:
(1) After the waste hydrochloric acid is subjected to homogenization adjustment, particles, colloid, bacteria and organic matters are removed through a waste hydrochloric acid ultrafiltration system, ultrafiltered concentrated water enters a concentrated liquid collecting tank, produced water enters a waste acid membrane separation system for membrane separation, concentrated water treated by the waste acid membrane separation system enters a concentrated water collecting tank, and produced water enters a mixing tank; the heavy metal ions are removed from the concentrated water in the concentrated liquid collecting tank through the integrated precipitation system 1 added with the coagulating sedimentation agent A, and then the concentrated water flows into the waste brine regulating tank;
(2) After the waste brine is subjected to homogenization adjustment, the waste brine enters an integrated precipitation system 2 added with a coagulating sedimentation agent B to remove heavy metal ions and particulate matters, then particles, colloid, bacteria and organic matters are removed through a waste brine ultrafiltration system, concentrated water of the waste brine ultrafiltration system flows back to a waste brine adjusting tank, and produced water enters a photocatalytic oxidation system to degrade available chlorine through photocatalytic reaction;
(3) Mixing produced water of the photocatalytic oxidation system in the step (2) with produced water of the waste hydrochloric acid ultrafiltration system in the step (1), removing alkaline substances through acid-base neutralization, introducing the degassed water into a primary membrane separation system, allowing concentrated water of the primary membrane separation system to flow back to a waste brine regulating tank, introducing the produced water into an MVR evaporation system for evaporation, allowing the evaporated crystal salt to be reused for titanium dioxide production, introducing the concentrated water into a secondary membrane separation system, and allowing the concentrated water of the secondary membrane separation system to flow back to the waste brine regulating tank;
the coagulating sedimentation agent A comprises alkaline substances, PAC and PAM;
the coagulating sedimentation agent B comprises PAC and PAM.
2. The system for treating waste hydrochloric acid and waste brine in titanium dioxide chloride production according to claim 1, wherein the photocatalytic oxidation system comprises a plurality of reaction devices connected in series, and a plurality of ultraviolet lamps are arranged in each reaction device.
3. The system for treating waste hydrochloric acid and waste brine in titanium dioxide chloride production according to claim 2, wherein the number of the reaction devices is 8-10.
4. The system for treating waste hydrochloric acid and waste brine in titanium dioxide chloride production according to claim 3, wherein 10-15 ultraviolet lamps are arranged in each reaction device, and the power of each ultraviolet lamp is 15-20w.
5. The system for treating waste hydrochloric acid and waste brine in the production of titanium dioxide chloride according to claim 1, wherein the waste hydrochloric acid treatment system further comprises a waste hydrochloric acid regulating tank, and the waste hydrochloric acid regulating tank is connected with a waste hydrochloric acid ultrafiltration system.
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