CN116395900A - Method for treating titanium pigment chloride slag water by membrane filtration process - Google Patents
Method for treating titanium pigment chloride slag water by membrane filtration process Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 82
- 239000002893 slag Substances 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 38
- 238000005374 membrane filtration Methods 0.000 title claims abstract description 22
- 239000001038 titanium pigment Substances 0.000 title claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 174
- 239000012528 membrane Substances 0.000 claims abstract description 120
- 238000001914 filtration Methods 0.000 claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 238000006386 neutralization reaction Methods 0.000 claims description 122
- 239000007788 liquid Substances 0.000 claims description 106
- 239000000706 filtrate Substances 0.000 claims description 48
- 238000004891 communication Methods 0.000 claims description 36
- 238000001728 nano-filtration Methods 0.000 claims description 28
- 238000003825 pressing Methods 0.000 claims description 25
- 238000005660 chlorination reaction Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002351 wastewater Substances 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 239000008267 milk Substances 0.000 claims description 7
- 210000004080 milk Anatomy 0.000 claims description 7
- 235000013336 milk Nutrition 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 239000012535 impurity Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 235000010215 titanium dioxide Nutrition 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 239000002006 petroleum coke Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940063656 aluminum chloride Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960002713 calcium chloride Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007805 chemical reaction reactant Substances 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 229960002337 magnesium chloride Drugs 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- NSYYPXSKPGPMBW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].Cl Chemical compound [O-2].[O-2].[Ti+4].Cl NSYYPXSKPGPMBW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- -1 vanadium pentoxide) Chemical compound 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/44—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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for treating titanium pigment chloride slag water by utilizing a membrane filtration process, which improves the structure of a ceramic membrane filter, shortens the path of part of channels of the ceramic membrane filter, improves the discharge efficiency of part of channels, effectively improves the water quality filtration speed on the basis of not reducing the filtration quality, greatly improves the continuous uninterrupted production time of the ceramic membrane filter on a large-scale production line, and reduces the frequency of backflushing, replacement or other production stopping maintenance.
Description
Technical Field
The invention relates to the technical field of chemical industry, relates to separation and recovery of chemical waste gas, in particular to a method for treating titanium pigment chlorination slag water by using a membrane filtration process, and particularly relates to a method for treating titanium pigment chlorination slag water by using an improved ceramic membrane filter in combination with an improved slag water step-by-step treatment process.
Background
At present, along with the tightening of environmental protection policies in China and the development requirements of the titanium white industry, the process of implementing zero emission by enterprises is more and more similar to that of the enterprises. The contradiction between treatment of slag water produced in the chlorination process of titanium dioxide is increasingly apparent, and the treatment of the chlorinated slag water becomes one of the important bottlenecks for restricting the development of titanium dioxide chloride enterprises. Therefore, in the production process of titanium dioxide by the chlorination process, solid waste residues produced in the chlorination process are sent into a dissolving tank to be dissolved through a cyclone dust collector, and the obtained slag water needs to realize the maximum and effective utilization of resources. The main component of the slag water is soluble metal chloride, and most of titanium white enterprises in the domestic titanium white production enterprises by the chloride process are most commonly treated by adopting the slag water and lime milk to perform neutralization reaction to obtain mixed wastewater of metal hydroxide precipitation and calcium chloride solution, and then the generated wastewater is subjected to simple filter pressing filtration and evaporation concentration to prepare calcium chloride.
However, the components contained in the titanium chloride white slag water are complex, impurities in the product can not be effectively removed only by simple filter-pressing filtration and evaporation concentration in the reaction process, a large amount of the components contained in the slag water and impurities generated after the reaction still remain in the solution, so that the purity of the produced calcium chloride product is low, the cost is low, the use is few, and meanwhile, the cost required by multi-effect evaporation concentration is high. In the whole, although the slag water can be treated in the direction, the cost is high and the effective utilization rate of resources is low. Moreover, equipment is severely worn during processing, and shutdown for cleaning and replacement of equipment is often required.
There have been many studies on the treatment method of titanium white slag water. For example, according to the report of Chinese patent publication CN112759164A, a method for recycling dust collection waste residue water of titanium dioxide prepared by a chlorination method is disclosed, which mainly comprises the following steps: insoluble matter separation and recovery, waste residue to be treatedSeparating and recovering high titanium slag and calcined coke by water through a first filtering device; hydrogen chloride is recovered, and the wastewater after passing through the first filtering device enters a hydrochloric acid stripping tower to extract hydrogen chloride; the titanium dioxide is recovered, the effluent of the hydrochloric acid stripping tower enters a second separation device through a pipeline, the pH value of the wastewater in the pipeline is regulated to 4.2-4.8, tiOCl 2 Hydrolysis to precipitate TiO 2 TiO in wastewater 2 Separating and recycling by a second separating device; recovering ferric oxide, wherein the effluent of the second separation device enters a first-stage reaction tank, the pH value of the first-stage reaction tank is regulated to 7-10, ferric hydroxide or ferrous hydroxide is precipitated and separated out, and then the ferric oxide is obtained through separation, dehydration and roasting of a third separation device; recovering the metal catalyst, wherein the supernatant of the primary reaction tank flows into the secondary reaction tank, the pH value is regulated to 10-12.5, and the metal hydroxide in the wastewater is completely precipitated, separated by a fourth separation device, dried, formed and roasted to obtain the metal catalyst; and recovering sodium chloride, wherein the supernatant of the secondary reaction tank passes through a nanofiltration device, and the sodium chloride is recovered through an evaporation crystallization device after nanofiltration to produce water.
However, the reaction cell during recovery of this method requires frequent cleaning of the nanofiltration system, such as back flushing and replacement of the wearing parts. And the treatment procedure is mechanized and long-range, and a flexible treatment scheme cannot be provided according to the later-stage requirements of the slag water.
Disclosure of Invention
From the above related art, there is a need to improve the treatment process of titanium pigment chloride slag water by the chlorination process.
The invention aims to solve the technical problem of providing a method for treating titanium dioxide chlorination slag water by using a membrane filtration technology, wherein the process can respectively select a chemical method and a category separation method according to the characteristics of different impurity components in the slag water to remove impurities, and finally obtain solid materials and high-quality brine which can be recycled and accord with the sustainable development concept.
According to the embodiment of the invention, the improved ceramic filter is combined with a plurality of flexibly detachable (optional or optional) chloridized slag-water separation processes, so that the requirement of continuously treating a large amount of slag water in the large-scale industrial production process is improved, and different combinations and screening can be performed according to different requirements of the slag water later recovery application in each step of the process, thereby effectively improving the recovery efficiency and ensuring the improvement of the treated water quality.
In a first aspect of the invention, a method for treating titanium pigment chloride slag water by using a membrane filtration process is provided, and comprises the following steps:
step 1): obtaining chlorinated slag water from chlorination equipment for producing titanium pigment by a chlorination method, and storing the chlorinated slag water;
step 2): the stored water in the step 1) is sent into a first diaphragm filter pressing device for filter pressing by a primary plate frame feeding pump, and the obtained filtrate enters a primary plate frame transfer tank;
step 3): pumping the filtrate in the primary plate frame transfer tank into a primary diversion trench through a primary filtrate intermediate pump, mixing the filtrate with lime milk, and then feeding the mixture into a primary neutralization tank, and regulating the pH value in the primary neutralization tank to be about 7-8; and
the method further comprises the steps of pumping the liquid, such as the neutralization water obtained in the step 3), into a ceramic membrane filtering device for filtering circulation (namely, the step 8) is performed; wherein the method comprises the steps of
The ceramic membrane filter equipment comprises a ceramic membrane filter, wherein the ceramic membrane filter comprises a ceramic matrix layer and a plurality of liquid inlet channels which are arranged in the ceramic matrix layer and are parallel to the longitudinal extension direction of the ceramic membrane filter, and the liquid inlet channels are provided with openings at two end faces of the ceramic membrane filter; and
at least one liquid collecting tank parallel to the liquid inlet channel, wherein
The liquid collecting tank has no opening on at least one of end surfaces in a longitudinal extending direction of the ceramic membrane filter; and is also provided with
The ceramic membrane filter further comprises a liquid communication groove which is arranged along the direction perpendicular to the liquid collecting groove, and the liquid communication groove is connected with the at least one liquid collecting groove; and is also provided with
The ceramic membrane filter is further provided with at least one opening on a side surface thereof, the opening being in communication with the liquid communication groove.
According to the scheme of the invention, the inventor improves the structure of the ceramic membrane filter according to experimental requirements and the use characteristics of the ceramic membrane filter, shortens the path of part of channels of the ceramic membrane filter, improves the discharge efficiency of the part of channels, effectively improves the water quality on the basis of not reducing the filtering quality, improves the filtering speed, greatly improves the time length of continuous uninterrupted production of the ceramic membrane filter on a large-scale production line, and reduces the frequency of backflushing, replacement or other production stopping maintenance.
In an alternative solution, the primary neutralization tank includes a first sub-neutralization tank, a second sub-neutralization tank, a third sub-neutralization tank, a fourth sub-neutralization tank, a fifth sub-neutralization tank and a sixth sub-neutralization tank which are sequentially arranged and connected, wherein during the performing of the step 3), a part of the neutralization liquid in the fourth sub-neutralization tank is pumped back to the first sub-neutralization tank by a neutralization liquid reflux pump, and sodium hydroxide is added in the fourth sub-neutralization tank by a dropwise adding manner, and the pH value is regulated to about 9 to 11, preferably 10 to 11, and most preferably 10.5 to 11.
The inventors have also found that for the neutralization reaction of the multi-stage neutralization tank and the overflow tank, the reflux operation of a part of the sub-overflow tank can improve the accuracy of the pH adjustment and control without significantly increasing the production cost. Under the condition of increasing the circulation flow, the effect of slowly regulating and controlling the pH value within a reasonable range can be applied.
In an alternative scheme, in the step 3), rainwater collected in a factory, workshop equipment cleaning water and floor cleaning wastewater are also added into the primary diversion trench.
In an alternative, the following step 4) is performed immediately after said step 3):
step 4): the neutralization liquid in the primary neutralization tank is sent into second diaphragm filter pressing equipment by a secondary plate frame feed pump, and corresponding filtrate is obtained;
after the step 4), the filtrate is pumped into the ceramic membrane filtration device for the filtration cycle.
In an alternative, the following step 5) is performed immediately after said step 4):
step 5): automatically flowing the filtrate obtained in the step 4) into a secondary baffling tank by gravity, adding sodium sulfate solution into the secondary baffling tank for full mixing, and then entering a secondary neutralization tank;
the secondary neutralization tank comprises a secondary first sub-overflow tank, a secondary second sub-overflow tank, a secondary third sub-overflow tank and a secondary fourth sub-overflow tank which are sequentially arranged and connected;
after the above step 5), the obtained filtrate is fed into the ceramic membrane filtration apparatus to perform the filtration cycle.
In the alternative, the following steps 6) and 7) are performed immediately after step 5):
step 6): the filtrate obtained in the step 5) is sent into a third diaphragm filter pressing system for filter pressing by a third plate frame feeding pump;
step 7): the filtrate automatically flows into a third baffling tank by gravity and is added with sodium carbonate solution for full mixing, and then enters a third neutralization tank, wherein the third neutralization tank comprises a third first sub overflow tank, a third second sub overflow tank, a third sub overflow tank and a third fourth sub overflow tank;
after the above step 7), pumping the obtained liquid into the ceramic membrane filtration device to perform the filtration cycle; and 3) conveying the filtrate obtained in the step 7) to a ceramic membrane circulation tank through a ceramic membrane feed pump, conveying the effluent obtained in the step 7) to the ceramic filter through the ceramic membrane circulation pump for circulating filtration, returning the obtained ceramic membrane concentrated water to the primary plate frame feed tank, and conveying the ceramic membrane clear liquid to the ceramic membrane water production tank.
In an alternative scheme, clear liquid in the ceramic membrane water producing tank is conveyed to a nanofiltration cartridge filter through a nanofiltration feed pump, and then conveyed to a nanofiltration system concentration salinity unit for filtration concentration through a nanofiltration high-pressure pump; the concentrated solution is sent back to the primary neutralization tank or the secondary neutralization tank, and the clear solution enters the nanofiltration water production tank.
In an alternative, wherein the cross-sectional shape of the inlet channel and/or liquid collection trough of the ceramic membrane filter is rectangular, substantially circular, elliptical, and/or polygonal.
In an alternative, wherein the ceramic membrane filter meets one or more of the following:
the ceramic matrix layer of the ceramic membrane filter comprises alumina;
the diameter of the ceramic membrane filter is phi 100-200mm;
the longitudinal length of the ceramic membrane filter is 1000-2500mm;
the number of the liquid communication grooves is 3 to 5;
the number of openings provided on the side surface thereof is 8 to 12.
In a further alternative and/or preferred embodiment of the invention, steps 1) to 8) above may be performed sequentially, or steps 1) to 9) may be performed sequentially.
The technical scheme and advantages of the present invention will be explained and illustrated in more detail below with reference to the detailed description. It should be understood that the matters presented in the description and the detailed description are only for clearly illustrating the technical solution of the present invention and the advantages thereof, and do not limit the scope of the present invention. Based on the disclosure of the specification, a person skilled in the art can obtain various changed technical solutions for various reasonable changes, and as long as the spirit of the invention is not deviated, all the changed technical solutions should be understood to be included in the protection scope of the invention.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosed embodiments and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain, without limitation, the disclosed embodiments.
FIG. 1 is a schematic diagram of an apparatus for the product and off-gas separation process of the present invention;
fig. 2 shows a side view and a schematic view in partial cross-section of a ceramic filter (ceramic cartridge) of an embodiment of the invention.
Fig. 3 shows a schematic perspective view of a ceramic filter according to an embodiment of the present invention.
Fig. 4 is an overall flow chart of the process of the present invention.
Reference numerals illustrate:
1-a titanium slag reservoir; 2-petroleum coke storage; 3-chlorine storage tank; 4-chlorination reaction furnace; 5-quench delivery pipe (with cyclone separator); 6-a dust collection buffer tank;
100-ceramic filter (ceramic filter cartridge); 101-a liquid inlet channel; 102-a ceramic matrix layer;
103-a liquid collection tank; 104-a liquid communication tank; 105-opening;
10-a primary plate frame feeding tank; 11-a primary plate frame feed pump; 12-a first membrane filter press apparatus; 13-a primary plate frame transfer pot; 14-primary filtrate is supplied externally; 144-pickling process in a chlorination workshop; 15-a primary filtrate intermediate pump; 16-a primary diversion trench; 17-a primary neutralization tank; 171-a first sub-neutralization tank; 171-a first sub-neutralization tank; 172-a second sub-neutralization tank; 173-a third sub-neutralization tank; 174-a fourth sub-neutralization tank; 175-a fifth sub-neutralization tank; 176-sixth sub-neutralization tank;
21-a secondary plate and frame feed pump; 23-secondary flow-folding grooves; 24-a secondary neutralization tank; 241-a secondary first sub overflow tank; 242-a secondary overflow tank; 243-a secondary third sub overflow pot; 244-a secondary fourth sub overflow pot;
32-a third membrane filter press system; 33-three times of flow-folding grooves; 34-three times of neutralization tanks; 341-a third sub overflow pot; 343-third second sub overflow tanks; 344-third fourth sub overflow tanks;
41-a ceramic membrane feed pump; 42-a ceramic membrane circulation tank; 43-ceramic membrane water producing tank; 44-nanofiltration cartridge filter; 45-nanofiltration high pressure pump; 46-nanofiltration of the product water tank.
Detailed Description
The present invention is described in more detail below to facilitate an understanding of the invention.
Before the description of the specific embodiments, it is to be noted that those skilled in the art, based on the teachings and teachings of the present disclosure, are able to select appropriate raw materials, and perform the relevant tests using the relevant test equipment and obtain the corresponding results, and that those skilled in the art, for raw materials not specifying a particular manufacturer or route, are able to select raw materials meeting the corresponding needs as reaction starting materials based on the disclosure and needs of the present specification. The reaction starting material for the process portion of the compounds is derived from the primary product synthesized in the preamble of the present invention.
The basic structure of the ceramic membrane filtration system adopted in the experiment of the invention is from a ceramic membrane filtration system (BNCM 61-6-A) provided by Shandong Bona (BoNa) group, and the total filtration area reaches 100m 2 The above, the treatment capacity is about 4 to 30 cubic meters (tons) per hour, depending on the feed pressure and fittings, and the apparatus can be fitted with a cleaning solution tank of over 2000 liters.
The ceramic filter (cartridge) used in the experiments of the present inventors was designed by the inventors and manufactured by the company of the university of refractory, rocyang, a group of delegated steels.
Basic parameters of ceramic membrane filter 100 employed in the embodiments of the present application. It should be noted that, according to the teachings of the present invention, those skilled in the art may adopt similar structures or ideas to construct a parallel arrangement which is not inconsistent or exclusive with the description of the present invention, thereby completing the present invention.
The basic material is as follows: alumina (Al) 2 O 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Pore diameter: 10-50 μm; preferably 50 μm, 40 μm or 30 μm; external dimensions: phi 160mm x 2000mm long: a liquid communication groove: 3-5 (examples detailed), openings (openings for mating with liquid communication channels, examples detailed): 8-12.
The neutralization tank and the baffle tank adopted by the embodiment of the invention are purchased from Xindi new energy sources and environmental equipment limited companies in Zhongshan. The neutralization tank size was 2000mm diameter x 5000mm long. It will be apparent to those skilled in the art that other forms of neutralization tank and baffle tank can be employed as long as the invention can be practiced according to the description.
The typical process of the invention mainly comprises a three-time neutralization device (system), a diaphragm filter pressing system, a ceramic membrane system, a nanofiltration system and a tail gas absorption system.
The process is to make the metal chloride collected by dust removal of cyclone separator according to the main production equipment chlorination furnace product in the chlorination workshop, and then to make the concentrated water obtained by post-treatment filtration and treatment of washing water by desalination water station to obtain the chlorination slag water (the components mainly comprise water, titanium dioxide, petroleum coke, hydrogen chloride, calcium chloride, magnesium chloride, manganese chloride, ferric chloride, ferrous chloride, aluminum chloride, vanadium oxide (such as vanadium pentoxide), etc.). It should be noted that the slag water component of the present invention is not limited to the chemical components described above and in the following table. The skilled artisan can also practice the present invention with similar compositions, or with wastewater from similar processes.
The composition of a typical chlorinated slag water is given in the following table (obtained as a function of the cationic content detected, expressed in% by weight; the balance being water, except for said impurities), can be approximated):
table 1: composition of typical chlorinated slag water of the invention
Example 1
Step 1): the metal chloride obtained from the main production equipment of the chlorination workshop is subjected to dust removal and collection by using a cyclone separator, and is washed by washing water (typical washing water can be from concentrated water obtained by treatment of a desalting water station) to prepare the chlorination slag water. A typical chlorination plant process and equipment can be seen in the schematic diagram of fig. 1.
The concentrated water obtained by post-treatment filtration and washing water treatment by a desalting water station is washed to prepare chloridized slag water (the components mainly comprise water, titanium dioxide, petroleum coke, hydrogen chloride, calcium chloride, magnesium chloride, manganese chloride, ferric chloride, ferrous chloride, aluminum chloride and vanadium oxide (such as vanadium pentoxide), and then the chloridized slag water is conveyed to a primary plate-frame feeding tank 10 for storage.
Step 2): the liquid stored in the step 1) is sent to a first diaphragm filter-pressing device (system) 12 for filter-pressing by a primary plate-and-frame feed pump 11, and inert slag (such as petroleum-containing coke and the like) can be used as fuel for steel plants and the like. The filtrate automatically flows into the primary plate-frame transfer tank 13 by gravity, and a part of filtrate (containing ferrous chloride) in the tank is sent to the pickling process 144 of the chlorination workshop for recycling through the primary filtrate external supply pump 14.
Step 3): the filtrate in the primary plate frame transfer tank is fed into the primary diversion trench 16 through the primary filtrate intermediate pump 15 to be added with lime milk for full mixing, and then enters the primary neutralization tank 17 (the primary neutralization tank 17 comprises 6 sub-neutralization tanks 171, 172, 173, 174, 175, 176) to be subjected to acid-base neutralization reaction by stirring, and the neutralization liquid reflux pump of the fourth sub-neutralization tank 174 can pump the neutralization liquid back to the first sub-neutralization tank 171 by the fourth sub-neutralization tank 174 to ensure the reaction to be full, and the pH value is adjusted to 7-8, preferably 7.5-8. Meanwhile, in order to strictly control the pH value, sodium hydroxide is added into the fifth sub-neutralization tank 175 to finely adjust the pH value to a fixed value.
Here, the inventors found that in this step, it is necessary to control the pH to not more than 11.5, preferably between 10 and 11, otherwise the aluminum hydroxide precipitate would dissolve. The dissolution of aluminum hydroxide can bring adverse effects in the subsequent impurity removal step, affecting the quality of the finally produced reclaimed water and the impurity removal rate. The pH adjustment may also be used in conjunction with improved ceramic membrane filters to further reduce the frequency of ceramic membrane filter plugging, cleaning backflushing, or replacement.
Here, the inventors found in the process study of treating waste gas, waste water and waste residue on a large scale in batches that waste water after washing of factory initial rainwater, accident water, each workshop apparatus and terrace is weakly acidic and cannot be directly discharged outside due to the process characteristics of titanium pigment by the chlorination process. Other acid wastewater of the production line is sent into the regulating tank for mixing, and is sent into the primary diversion trench 16 by the wastewater lifting pump for recycling. Not only can solve the problem of acid wastewater treatment, but also can effectively utilize chloride ions in the wastewater.
The process improvement enables most of the process wastewater in the production line of the inventor to be effectively treated and utilized, and the process wastewater discharge is improved towards the factory process.
In example 1, the neutralization water passing through the primary neutralization tank 17 may directly enter the ceramic filter 100 of the present invention, but it may also be preferable that the primary neutralization tank 17 of the present invention enters the ceramic membrane circulation system (step 8) after passing through steps 4 to 7) described in the following examples.
Step 8) may be directly performed in this embodiment 1. The neutralization water passing through the primary neutralization tank 17 enters a ceramic membrane filtration system, is conveyed to a ceramic membrane circulation tank 42 by a ceramic membrane feed pump 41, and the effluent of the previous step is conveyed to a ceramic filter 100 by the ceramic membrane circulation pump for circulating filtration. The concentrated ceramic membrane water can be returned to the primary plate frame feed tank 10, and the clear ceramic membrane liquid enters the ceramic membrane water producing tank 43.
The inventors have surprisingly found that this embodiment enables the direct pumping of the neutralized water or semi-finished filtered water of steps 1) to 3) directly into a ceramic membrane filtration system for filtration cycle without having to go through the fine filtration and neutralization of steps 4) to 7), and can continuously maintain the use of the neutralization and ceramic filtration device. In part, because of the improved ceramic filter 100 employed in the present application. As will be described in detail below.
Fig. 2 and 3 show the structure of the ceramic filter 100 employed in the present embodiment, wherein fig. 2 is a side view and a sectional view taken from section A-A.
As shown, ceramic matrix layer 102 is included in the cross section of ceramic membrane filter 100, while liquid communication channel 104 is included in the cross section of ceramic membrane filter 100 in the cross section.
In the cross section of the ceramic membrane filter 100, the ceramic matrix layer 102 is provided with inlet channels 101 (only a part is shown).
Further according to the drawing, a plurality of liquid collection grooves 103 (only a part is shown) are provided in parallel with the liquid inlet passage 101, and a plurality of liquid communication grooves 104 are provided, the liquid communication grooves 104 being connected to and penetrating the plurality of liquid collection grooves 103. The extending directions of the liquid communication groove 104 and the plurality of liquid collection grooves 103 are perpendicular to each other. As shown in fig. 2 and 3, the ceramic membrane filter 100 is provided with a plurality of liquid collection grooves 103 which are not open on at least one of (both) end faces in the extending direction, as can be seen. Openings 105 are provided in the side surface of the ceramic membrane filter 100 corresponding to the liquid communication grooves 104 (for example, 4 or 8 openings 105 are provided if there are four liquid communication grooves 104). In other words, the openings 105 may be in communication with the liquid communication grooves 104 on the side, and the number of the two is the same; alternatively, the number of openings is twice the number of liquid communication grooves, that is, one liquid communication groove 104 extends to both end sides of the ceramic membrane filter 100 and has one opening on each of both end sides.
According to one of the design concepts of the present application, the cross-sectional shape of the inlet channel and/or the liquid collecting channel may be rectangular, for example, but may also be substantially circular, oval, polygonal, etc. The liquid communication channel 104 may for example be connected to at least one liquid collection channel 103, which liquid collection channel 103 is substantially parallel to the inlet channel 101 and has no openings on the end surfaces. The cross-sectional shape of the liquid communication groove 104 may be circular, elliptical, polygonal, or the like. By providing the liquid communication groove 104 and the liquid collection groove 103, the maximum distance from the inlet flow path to the surface of the permeation side can be shortened, the surface area of the permeation side can be increased, and the permeation flux can be improved. At the same time, even if the filtrate quality is poor (e.g., contains more particulate impurities), the probability of clogging of the particles in the ceramic filter is greatly reduced, so that the frequency of ceramic filter repair or shutdown backflushing is greatly reduced.
As a matter of further description of the ceramic filter, in the present application and embodiment, the liquid collection tank 103 is separated from the liquid inlet channel 101 by the ceramic matrix layer 102. As shown, the fluid communication slots 104 extend across the entire ceramic matrix layer 102 from one side edge of the monolithic ceramic membrane filter 100 to the other side. Further, although a fixed number of the liquid communication grooves 104 are provided in the embodiment, the number thereof may be, for example, 2 to 8.
In addition, a liquid communication groove 104 with an opening 105 is provided on the side of the ceramic base layer 102, so that the distance from the surface of the membrane layer to the permeable layer becomes smaller. The throughput is improved without affecting the filtration efficiency.
Comparative example 1
Comparative example 1 the same steps 1) to 3) as in example 1 were carried out, except that a common ceramic membrane filter was used in comparative example 1. The common ceramic membrane filter herein refers to the liquid collection tank 103, the liquid communication tank 104, and the specific openings 105 described without the ceramic membrane filter 100, and other parameters are the same as those of the ceramic filter of example 1, and the ceramic membrane filter is still manufactured by the institute of refractory material of the steel group in order to demonstrate test efficiency.
Under the condition of mass production test, the comparative production conditions of the two are as follows:
table 2: filtration process of different ceramic filter devices
From the examples and comparative examples, the ceramic filter of example 1 can meet continuous operation for a longer period of time without backflushing cleaning, while satisfying substantially the same filtering effect. Meanwhile, the flux (or water treatment capacity) of the ceramic filter of example 1 can be improved by nearly 10% as compared to comparative example 1.
Example 2
In this embodiment, after step 1) to step 3) of embodiment 1 are performed, step 4) described below is performed, and then step 8) is performed.
Step 4): the neutralization solution in the primary neutralization tank 17 is sent to a second diaphragm filter-pressing system 22 for filter pressing by a secondary plate-and-frame feed pump 21, and the filter residues also contain hydroxide sediment (mainly magnesium hydroxide, manganese hydroxide, ferric hydroxide and aluminum hydroxide) which can be sent to a building material product factory as raw materials, and the main component of the generated filtrate is calcium chloride solution.
This embodiment 2 may then execute step 8). The filter-pressed water passing through the second diaphragm filter-pressing system 22 enters a ceramic membrane filter system, is conveyed to a ceramic membrane circulating tank 42 by a ceramic membrane feed pump 41, and the effluent of the previous step is conveyed to a ceramic filter 100 by the ceramic membrane circulating pump for circulating filtration. The concentrated ceramic membrane water can be returned to the primary plate frame feed tank 10, and the clear ceramic membrane liquid enters the ceramic membrane water producing tank 43.
Example 3
In this embodiment, after steps 1 to 4) of embodiment 2 are performed, step 5) described below is performed, and then step 8) is performed.
Step 5): the filtrate obtained in the step 4 automatically flows into a secondary baffling tank 23 by gravity and is added with sodium sulfate solution for full mixing, and then enters a secondary neutralization tank 24 (adopting a step-by-step overflow process, comprising four sub overflow tanks, namely a secondary first sub overflow tank and a secondary fourth sub overflow tank 241, 242, 243 and 244) for double decomposition reaction by stirring, so as to generate calcium sulfate precipitate and sodium chloride solution.
Example 3 may next perform step 8). The filter-pressed water passing through the secondary neutralization tank 24 enters a ceramic membrane filtration system, is conveyed to a ceramic membrane circulation tank 42 by a ceramic membrane feed pump 41, and the effluent of the previous step is conveyed to a ceramic filter 100 by the ceramic membrane circulation pump for circulating filtration. The concentrated ceramic membrane water can be returned to the primary plate frame feed tank 10, and the clear ceramic membrane liquid enters the ceramic membrane water producing tank 43.
Example 4
In this embodiment, after steps 1) to 5) of embodiment 3 are performed, steps 6) and 7) described below are performed, and then steps 8) and 9) are performed.
Step 6): and (3) conveying the filtrate obtained in the step (5) into a third diaphragm filter pressing system (32) for filter pressing by a third plate and frame feed pump (31), wherein the solid filter residue of calcium sulfate can be used as a raw material to be conveyed to a gypsum acid making plant, and the filtrate mainly comprises a mixed solution of sodium chloride and saturated calcium sulfate.
Step 7): the filtrate is gravity-fed into a third baffling tank 33 and added with sodium carbonate solution for full mixing, and then enters a third neutralization tank 34 (comprising four sub overflow tanks from a third sub overflow tank to a third sub overflow tank 341, 342, 343, 344) for complete reaction by stirring, so as to generate calcium carbonate precipitation suspension.
Step 8): and then the filtrate in the step 7 is conveyed to a ceramic membrane circulation tank 42 through a ceramic membrane feed pump 41, and the effluent in the step 7 is circularly filtered in a ceramic filter 100 through the ceramic membrane circulation pump. The concentrated ceramic membrane water can be returned to the primary plate frame feed tank 10, and the clear ceramic membrane liquid enters the ceramic membrane water producing tank 43.
Step 9): the clear liquid in the ceramic membrane water producing tank is conveyed to a nanofiltration cartridge filter through a nanofiltration feed pump, and then conveyed to a nanofiltration system concentration salt separation unit for filtration and concentration through a nanofiltration high-pressure pump. And (3) the concentrated solution can be selectively sent back to the primary neutralization tank or the secondary neutralization tank according to the result of laboratory sampling analysis on the concentration of metal ions, and clear liquid enters the nanofiltration water production tank.
Optionally, the invention can be added to the salt-dissolving process of a chlor-alkali factory, wherein clear liquid in the nanofiltration water production tank is sodium chloride solution with little impurity (salt possibly containing a small amount of sodium sulfate or sulfate ions) and can be used as a raw material for the salt-dissolving process of the chlor-alkali factory.
In any of the embodiments, in order to prevent the acid gas from directly discharging to the atmosphere to cause environmental pollution, an induced draft fan is connected with a tail gas absorption system, and the acid gas is washed by alkali liquor and then discharged after reaching the standard.
All process flows shown and described in the above embodiments of the present invention can be seen in the description of fig. 4. According to the embodiments of the present invention, 1 of the above embodiments may be reasonably selected according to different requirements (e.g., impurity content and application scenario) for the filtrate, or different embodiments may be superimposed.
Comparative example 2
In comparative example 2, the same steps 1), 2), 4) to 9) as in example 4 were performed. In contrast, the neutralization solution reflux pump not provided in the fourth sub-neutralization tank 174 in step 3) may return the neutralization solution from the fourth sub-neutralization tank 174 to the first sub-neutralization tank 171 to ensure sufficient reaction, and the pH adjustment of 7 to 8 is not provided. Then, sodium hydroxide solution is added dropwise to the sixth neutralization tank 176.
As a result, after the process of step 9) was completed, the mass of Al ion reduced hydroxide in the obtained cleaning liquid was tested to exceed 0.1wt%, whereas the recycling process of the precisely controlled pH in example 1 was such that the mass of impurities of Al ion reduced hydroxide was less than 0.01wt%.
The inventors do not wish to be bound by any theory. However, from comparison of the returned experimental data, it is possible that the neutralization liquid reflux pump provided in the fourth sub-neutralization tank 174 may circulate the neutralization liquid back to the first sub-neutralization tank 171 from the fourth sub-neutralization tank 174, which is advantageous for slow adjustment of the pH value of the circulating liquid, and that the pH value may be instantaneously raised to a state where Al ions are brought into solution without the existence of the circulation condition due to strong alkalinity of lime milk or sodium hydroxide itself, so that it cannot be treated in the subsequent treatment step of the ceramic filter or the like. In the circulating state, the pH value detection change is slower, and the addition amount and the addition speed of lime milk can be adjusted to be smaller, so that the monitoring and the accurate control of the pH value are facilitated.
According to the embodiments and technical content described in the specification of the present invention, the present invention can provide at least the following technical solutions: although the present disclosure includes specific embodiments, it will be obvious to those skilled in the art that various substitutions and modifications may be made in form and detail without departing from the spirit and scope of the present claims and their equivalents. The embodiments described herein should be considered in an illustrative sense only and not for the purpose of limitation. The description of features and aspects in each embodiment is considered to apply to similar features and aspects in other embodiments. Therefore, the scope of the present disclosure should not be limited by the specific description, but by the claims, and all changes within the scope of the claims and the equivalents thereof are to be construed as being included in the technical solutions of the present disclosure.
The invention at least provides the following technical scheme:
step 1): obtaining chlorinated slag water from chlorination equipment for producing titanium pigment by a chlorination method, and storing the chlorinated slag water;
step 2): the stored water in the step 1) is sent into a first diaphragm filter pressing device for filter pressing by a primary plate frame feeding pump, and the obtained filtrate enters a primary plate frame transfer tank;
step 3): pumping the filtrate in the primary plate frame transfer tank into a primary diversion trench through a primary filtrate intermediate pump, mixing the filtrate with lime milk, and then feeding the mixture into a primary neutralization tank, and regulating the pH value in the primary neutralization tank to be about 7-8; and
the method further comprises the steps of pumping the liquid, such as the neutralization water obtained in the step 3), into ceramic membrane filtering equipment for filtering circulation; wherein the method comprises the steps of
The ceramic membrane filter equipment comprises a ceramic membrane filter, wherein the ceramic membrane filter comprises a ceramic matrix layer and a plurality of liquid inlet channels which are arranged in the ceramic matrix layer and are parallel to the longitudinal extension direction of the ceramic membrane filter, and the liquid inlet channels are provided with openings at two end faces of the ceramic membrane filter; and
at least one liquid collecting tank parallel to the liquid inlet channel, wherein
The liquid collecting tank has no opening on at least one of end surfaces in a longitudinal extending direction of the ceramic membrane filter; and is also provided with
The ceramic membrane filter further comprises a liquid communication groove which is arranged along the direction perpendicular to the liquid collecting groove, and the liquid communication groove is connected with the at least one liquid collecting groove; and is also provided with
The ceramic membrane filter is further provided with at least one opening on a side surface thereof, the opening being in communication with the liquid communication groove.
The method according to scheme 2, wherein the primary neutralization tank comprises a first sub-neutralization tank, a second sub-neutralization tank, a third sub-neutralization tank, a fourth sub-neutralization tank, a fifth sub-neutralization tank and a sixth sub-neutralization tank which are sequentially arranged and connected, a part of the neutralization solution in the fourth sub-neutralization tank is pumped back to the first sub-neutralization tank by a neutralization solution reflux pump during the step 3), and sodium hydroxide is added in the fourth sub-neutralization tank by dropping, and the pH value is regulated to about 9 to 11, preferably 10 to 11, and most preferably 10.5 to 11.
Scheme 4. The method according to the above scheme wherein said step 3) is followed by the following step 4):
step 4): the neutralization liquid in the primary neutralization tank is sent into second diaphragm filter pressing equipment by a secondary plate frame feed pump, and corresponding filtrate is obtained;
after the step 4), the filtrate is pumped into the ceramic membrane filtration device for the filtration cycle.
Scheme 5. The method according to any one of the preceding schemes, wherein said step 4) is followed by the following step 5):
step 5): automatically flowing the filtrate obtained in the step 4) into a secondary baffling tank by gravity, adding sodium sulfate solution into the secondary baffling tank for full mixing, and then entering a secondary neutralization tank;
the secondary neutralization tank comprises a secondary first sub-overflow tank, a secondary second sub-overflow tank, a secondary third sub-overflow tank and a secondary fourth sub-overflow tank which are sequentially arranged and connected;
after the above step 5), the obtained filtrate is fed into the ceramic membrane filtration apparatus to perform the filtration cycle.
Scheme 6. The method according to any one of schemes 1 to 5, wherein said step 5) is followed by the following steps 6) and 7):
step 6): the filtrate obtained in the step 5) is sent into a third diaphragm filter pressing system for filter pressing by a third plate frame feeding pump;
step 7): the filtrate automatically flows into a third baffling tank by gravity and is added with sodium carbonate solution for full mixing, and then enters a third neutralization tank, wherein the third neutralization tank comprises a third first sub overflow tank, a third second sub overflow tank, a third sub overflow tank and a third fourth sub overflow tank;
after the above step 7), pumping the obtained liquid into the ceramic membrane filtration device to perform the filtration cycle; and 3) conveying the filtrate obtained in the step 7) to a ceramic membrane circulation tank through a ceramic membrane feed pump, conveying the effluent obtained in the step 7) to the ceramic filter through the ceramic membrane circulation pump for circulating filtration, returning the obtained ceramic membrane concentrated water to the primary plate frame feed tank, and conveying the ceramic membrane clear liquid to the ceramic membrane water production tank.
The method according to any one of the schemes 1 to 6, wherein the clear liquid in the ceramic membrane water producing tank is conveyed to a nanofiltration cartridge filter through a nanofiltration feed pump and then conveyed to a nanofiltration system concentration salt unit for filtration concentration by a nanofiltration high-pressure pump; the concentrated solution is sent back to the primary neutralization tank or the secondary neutralization tank, and the clear solution enters the nanofiltration water production tank.
The method according to any one of aspects 1 to 7, wherein the cross-sectional shape of the liquid inlet channel and/or liquid collection tank of the ceramic membrane filter is rectangular, substantially circular, elliptical, and/or polygonal.
The method of any one of claims 1 to 8, wherein the ceramic membrane filter meets one or more of the following:
the ceramic matrix layer of the ceramic membrane filter comprises alumina;
the diameter of the ceramic membrane filter is phi 100-200mm;
the longitudinal length of the ceramic membrane filter is 1000-2500mm;
the number of the liquid communication grooves is 3 to 5;
the number of openings provided on the side surface thereof is 8 to 12.
Claims (9)
1. A method for treating titanium pigment chloride slag water by using a membrane filtration process comprises the following steps:
step 1): obtaining chlorinated slag water from chlorination equipment for producing titanium pigment by a chlorination method, and storing the chlorinated slag water;
step 2): the stored water in the step 1) is sent into a first diaphragm filter pressing device for filter pressing by a primary plate frame feeding pump, and the obtained filtrate enters a primary plate frame transfer tank;
step 3): pumping the filtrate in the primary plate frame transfer tank into a primary diversion trench through a primary filtrate intermediate pump, mixing the filtrate with lime milk, and then feeding the mixture into a primary neutralization tank, and regulating the pH value in the primary neutralization tank to be about 7-8; and
the method further comprises the steps of pumping the liquid, such as the neutralization water obtained in the step 3), into ceramic membrane filtering equipment for filtering circulation; wherein the method comprises the steps of
The ceramic membrane filter equipment comprises a ceramic membrane filter, wherein the ceramic membrane filter comprises a ceramic matrix layer and a plurality of liquid inlet channels which are arranged in the ceramic matrix layer and are parallel to the longitudinal extension direction of the ceramic membrane filter, and the liquid inlet channels are provided with openings at two end faces of the ceramic membrane filter; and
at least one liquid collecting tank parallel to the liquid inlet channel, wherein
The liquid collecting tank has no opening on at least one of end surfaces in a longitudinal extending direction of the ceramic membrane filter; and is also provided with
The ceramic membrane filter further comprises a liquid communication groove which is arranged along the direction perpendicular to the liquid collecting groove, and the liquid communication groove is connected with the at least one liquid collecting groove; and is also provided with
The ceramic membrane filter is further provided with at least one opening on a side surface thereof, the opening being in communication with the liquid communication groove.
2. The method according to claim 1, wherein the primary neutralization tank comprises six sub-neutralization tanks, a first sub-neutralization tank, a second sub-neutralization tank, a third sub-neutralization tank, a fourth sub-neutralization tank, a fifth sub-neutralization tank and a sixth sub-neutralization tank, which are sequentially arranged and connected in this order, wherein during the proceeding of the step 3), a part of the neutralization liquid of the fourth sub-neutralization tank is pumped back to the first sub-neutralization tank by a neutralization liquid reflux pump, and sodium hydroxide is added dropwise to the fourth sub-neutralization tank to adjust the pH to about 9 to 11, preferably to 10 to 11, most preferably to 10.5 to 11.
3. The method according to claims 1 to 2, wherein in said step 3), plant-collected rainwater, plant-equipment cleaning water, and floor cleaning wastewater are also added to said primary launder.
4. A method according to any one of claims 1 to 3, wherein said step 3) is followed by the following step 4):
step 4): the neutralization liquid in the primary neutralization tank is sent into second diaphragm filter pressing equipment by a secondary plate frame feed pump, and corresponding filtrate is obtained;
after the step 4), the filtrate is pumped into the ceramic membrane filtration device for the filtration cycle.
5. The method according to any one of claims 1 to 4, wherein said step 4) is followed by the following step 5):
step 5): automatically flowing the filtrate obtained in the step 4) into a secondary baffling tank by gravity, adding sodium sulfate solution into the secondary baffling tank for full mixing, and then entering a secondary neutralization tank;
the secondary neutralization tank comprises a secondary first sub-overflow tank, a secondary second sub-overflow tank, a secondary third sub-overflow tank and a secondary fourth sub-overflow tank which are sequentially arranged and connected;
after the above step 5), the obtained filtrate is fed into the ceramic membrane filtration apparatus to perform the filtration cycle.
6. The method according to any one of claims 1 to 5, wherein said step 5) is followed by the following steps 6) and 7):
step 6): the filtrate obtained in the step 5) is sent into a third diaphragm filter pressing system for filter pressing by a third plate frame feeding pump;
step 7): the filtrate automatically flows into a third baffling tank by gravity and is added with sodium carbonate solution for full mixing, and then enters a third neutralization tank, wherein the third neutralization tank comprises a third first sub overflow tank, a third second sub overflow tank, a third sub overflow tank and a third fourth sub overflow tank;
after the above step 7), pumping the obtained liquid into the ceramic membrane filtration device to perform the filtration cycle; and 3) conveying the filtrate obtained in the step 7) to a ceramic membrane circulation tank through a ceramic membrane feed pump, conveying the effluent obtained in the step 7) to the ceramic filter through the ceramic membrane circulation pump for circulating filtration, returning the obtained ceramic membrane concentrated water to the primary plate frame feed tank, and conveying the ceramic membrane clear liquid to the ceramic membrane water production tank.
7. The method according to any one of claims 1 to 6, wherein the clear liquid in the ceramic membrane water production tank is conveyed to a nanofiltration cartridge filter through a nanofiltration feed pump and then conveyed to a nanofiltration system concentration salinity unit by a nanofiltration high-pressure pump for filtration concentration; the concentrated solution is sent back to the primary neutralization tank or the secondary neutralization tank, and the clear solution enters the nanofiltration water production tank.
8. The method of any one of claims 1 to 7, wherein the cross-sectional shape of the liquid inlet channel and/or liquid collection trough of the ceramic membrane filter is rectangular, substantially circular, elliptical, and/or polygonal.
9. The method of any one of claims 1 to 8, wherein the ceramic membrane filter meets one or more of the following:
the ceramic matrix layer of the ceramic membrane filter comprises alumina;
the diameter of the ceramic membrane filter is phi 100-200mm;
the longitudinal length of the ceramic membrane filter is 1000-2500mm;
the number of the liquid communication grooves is 3 to 5;
the number of openings provided on the side surface thereof is 8 to 12.
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| CN202310514986.3A CN116395900A (en) | 2023-05-09 | 2023-05-09 | Method for treating titanium pigment chloride slag water by membrane filtration process |
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