CN115448512A - Method for treating wastewater produced by producing white carbon black by carbonization method - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000002351 wastewater Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 116
- 239000006229 carbon black Substances 0.000 title claims abstract description 103
- 238000003763 carbonization Methods 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 151
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 131
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 128
- 239000012528 membrane Substances 0.000 claims abstract description 95
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 65
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 64
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 64
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 claims abstract description 52
- 238000001704 evaporation Methods 0.000 claims abstract description 50
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 49
- 238000001728 nano-filtration Methods 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 77
- 239000010703 silicon Substances 0.000 claims description 77
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 61
- 230000008020 evaporation Effects 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000002455 scale inhibitor Substances 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000010802 sludge Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 12
- 238000004065 wastewater treatment Methods 0.000 abstract description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 57
- 239000000243 solution Substances 0.000 description 26
- 235000002639 sodium chloride Nutrition 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000701 coagulant Substances 0.000 description 9
- 159000000000 sodium salts Chemical class 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 235000010344 sodium nitrate Nutrition 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 241000227425 Pieris rapae crucivora Species 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- -1 or sodium sulfate Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229960004029 silicic acid Drugs 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
-
- 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
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by 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
- C02F1/442—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
- C02F1/44—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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/60—Silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of chemical wastewater treatment, in particular to a method for treating wastewater produced by carbonizing white carbon black. The method comprises the steps of 1) cooling the wastewater to be treated and then carrying out electrolytic desiliconization treatment; 2) Carrying out ultrafiltration treatment on the wastewater subjected to electrolytic desiliconization in the step 1) to provide ultrafiltration treatment water; 3) Subjecting the ultrafiltration treatment water provided in the step 2) to reverse osmosis treatment to provide first produced water and first concentrated water; 4) Carrying out nanofiltration membrane treatment on the first concentrated water provided by the step 3) to provide second produced water and second concentrated water; 5) Evaporating the second produced water provided in step 4) to provide sodium bicarbonate; 6) Evaporating the second concentrated water provided by the step 5) to provide sodium carbonate. The method greatly reduces the treatment cost of the white carbon black wastewater produced by the carbonization method, and really realizes zero discharge of the white carbon black production wastewater produced by the carbonization method.
Description
Technical Field
The invention relates to the technical field of chemical wastewater treatment, in particular to a method for treating wastewater produced by carbonizing white carbon black.
Background
White carbon black is a common name of artificially synthesized hydrated silica powder, and the name of white carbon black is derived from the fact that white carbon black has the performance similar to that of carbon black for reinforcing rubber. Carbon black has a long history as a reinforcing agent for rubber, and since carbon black as a black reinforcing agent is limited in some application fields where color is required, studies have been made to chemically synthesize an active amorphous silica instead of carbon black. Amorphous silica is another excellent reinforcing filler, following carbon black, and is conventionally referred to as white carbon, because of its white color.
The white carbon black can be precipitated white carbon black and gas-phase white carbon black according to the production mode, the chemical name of the precipitated white carbon black is precipitated hydrated silicon dioxide, and the molecular formula is SiO 2 ·nH 2 O。
The synthetic process of precipitated silica is essentially the process of converting dense crystalline silica (quartz sand) into loose amorphous hydrated silica, i.e. SiO 2 →SiO 2 ·nH 2 And O. The specific process can be mainly divided into the traditional precipitation method and the gel method, wherein the traditional precipitation method is that the silicate is acidified to obtain the SiO which is loose and dispersed and is precipitated in a flocculent structure 2 The main raw materials of the method are sodium silicate and various inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and the method has the advantages of easily available raw materials, simple production flow, low energy consumption and low investment. The waste water is mainly high-salinity water containing sodium sulfate, sodium chloride and sodium nitrate.
The production method of the precipitated white carbon black belongs to the production category of the precipitated white carbon black, but the production raw materials and the production process of the precipitated white carbon black are different from the production method of the traditional precipitated white carbon black, carbon dioxide gas is adopted to carry out carbonization operation through soluble silicate solution, precipitated silicon dioxide, sodium bicarbonate and sodium carbonate are generated through reaction, pre-filtration is firstly carried out after the reaction is finished, the sodium bicarbonate and the sodium carbonate in the product are removed by using acid aqueous solution, and the white carbon black product can be obtained through filtration and drying.
The raw material for producing white carbon black by carbonization method is various CO-containing 2 Exhaust gas of (2), a large amount of CO 2 The recycling of the waste gas has far-reaching significance for reducing carbon emission, and is the future development direction of the precipitated white carbon black. The production process can produce white carbon black product with high reinforcing performance and low production costGood dispersion performance, and remarkable social and environmental benefits.
The basic process flow diagram is shown in figure 4.
In the production process of white carbon black by a carbonization method, two kinds of waste water can appear, the first kind is mother liquor (waste water), and the mother liquor amount is about 8m 3 T, wherein the sodium bicarbonate and sodium carbonate contents are about 5.7%, 1.2%, respectively; the second is washing water (waste water) with an amount of about 17m 3 T, wherein the sodium bicarbonate and sodium carbonate contents are about 3.4%, 0.8%, respectively. The total amount of the waste water after mixing the mother liquor and the washing water is 25m 3 The average contents of sodium bicarbonate and sodium carbonate were about 4.1% and 0.9%, respectively. Meanwhile, the mother liquor and the washing wastewater also contain colloidal silica, soluble silicon and other elemental substances, and table 1 shows the content of a part of elemental substances in the white carbon black wastewater by the carbonization method.
TABLE 1
| Item | Unit | White carbon black washing water | White carbon black mother liquor |
| Cl | mg/L | ＜1000 | ＜1000 |
| F | mg/L | ＜1 | ＜1 |
| Ca 2+ | mg/L | ＜1 | ＜1 |
| Mg 2+ | mg/L | ＜1 | ＜1 |
| Al 3+ | mg/L | ≤0.05 | ≤0.05 |
| Fe 2+ | mg/L | ≤0.05 | ≤0.05 |
| Mn | mg/L | ≤0.05 | ≤0.05 |
| Soluble silicon | mg/L | ≥200 | ≥300 |
In the prior art, only two methods are available for treating the traditional precipitated white carbon black wastewater. The first method is direct evaporation, and the direct evaporation has the defects of large investment and high operation cost. No matter the production line of 30000 tons of common precipitated white carbon black produced in one year adopts multi-effect evaporation or MVR evaporation, the one-time investment is more than 5500 ten thousand yuan, the cost of each ton of white carbon black is increased by more than 900 yuan, which accounts for about 35% of the production cost, and the production line is unacceptable for production enterprises. The second method adopts electric desiliconization, membrane separation concentration and evaporation, but the application range is limited to the common precipitation white carbon black produced by using inorganic acid as a raw material, such as: the precipitated silica produced by using sulfuric acid, hydrochloric acid or nitric acid only contains single inorganic salt, so that the concentration and separation are relatively simple, and in addition, other methods for more effectively treating the precipitated silica wastewater do not exist. To date, no production enterprise at home and abroad really realizes the zero discharge of the white carbon black wastewater treatment, and the treatment of the white carbon black production wastewater by the carbonization method is the technical blank at present.
From the above, how to provide a low-cost method for treating white carbon black wastewater by using a carbonization method to realize zero discharge of white carbon black wastewater by using the carbonization method is a technical problem to be solved urgently at present.
Disclosure of Invention
In view of the defects of the prior art, the existing white carbon black wastewater treatment technology can only treat the common (sulfuric acid method, hydrochloric acid method and nitric acid method) precipitated white carbon black production wastewater, and has the problems of high treatment device requirement, large investment and high treatment cost, so that the requirements of production enterprises cannot be met, and a method for treating the white carbon black wastewater by the carbonization method is not introduced and applied in the prior art and actual production. Therefore, the invention aims to provide a method for treating wastewater produced by carbonizing white carbon black.
The purpose of the invention can be realized by the following technical scheme: the invention provides a method for treating wastewater produced by producing white carbon black by a carbonization method, which comprises the following steps:
1) Cooling the wastewater to be treated, and then carrying out electrolytic desiliconization treatment;
2) Carrying out ultrafiltration treatment on the wastewater subjected to electrolytic desiliconization in the step 1) to provide ultrafiltration treatment water;
3) Subjecting the ultrafiltration treatment water provided in the step 2) to reverse osmosis treatment to provide first produced water and first concentrated water;
4) Carrying out nanofiltration membrane treatment on the first concentrated water provided by the step 3) to provide second produced water and second concentrated water;
5) Evaporating the second produced water provided in step 4) to provide sodium bicarbonate;
6) Evaporating the second concentrated water provided by the step 5) to provide sodium carbonate.
In some embodiments of the invention, the wastewater to be treated in the step 1) is electrolyzed under the current of 20-40A and the voltage of 15-40V, and metal ions dissolved out from the metal anode are hydrolyzed in the water to generate flocculation; the anode produces oxygen and the cathode produces hydrogen, which after electrolysis, the colloidal and soluble silicon become flocs, which are oxides and hydroxides of metals.
In some embodiments of the invention, step 2) is performed by adding a silicon removing agent into the wastewater after electrolytic silicon removal in step 1) and then performing ultrafiltration treatment; preferably, the dosage of the silicon removing agent is 0.15-0.2 kg/t water.
In some embodiments of the invention, flocs are also obtained after the ultrafiltration treatment in step 2), and the flocs are subjected to solid-liquid separation to obtain dewatered sludge.
In some embodiments of the invention, in step 3), the ultrafiltration treatment water provided in step 2) is added with a high silica scale inhibitor and a reducing agent and then subjected to reverse osmosis treatment; preferably, the dosage of the high-silicon scale inhibitor is 0.0015 to 0.0025kg/t water; the reducing agent is selected from sodium bisulfite; the dosage of the reducing agent is 0.004-0.005 kg/t.
In some embodiments of the invention, the first water produced in step 3) is reused for production.
In some embodiments of the invention, the evaporation condensate obtained after the evaporation treatment in step 4) and step 5), respectively, is reused for production.
In some embodiments of the present invention, the second concentrated water comprises a sodium carbonate solution, and the sodium carbonate solution comprises sodium bicarbonate.
In some embodiments of the invention, the sodium bicarbonate is present in an amount of 50 to 85g/l; the content of the sodium carbonate is 80-100 g/l.
In some embodiments of the invention, the second water production comprises a sodium bicarbonate solution; preferably, the concentration of the sodium bicarbonate is 50-85 g/l; the sodium carbonate solution contains sodium carbonate, and the concentration of the sodium carbonate is 0.2-0.4 g/l.
Drawings
FIG. 1 is a process flow diagram of the treatment of wastewater from the production of white carbon black by the carbonization method of the present invention.
FIG. 2 is a schematic diagram of the electrical desilication of the present invention.
FIG. 3 is a structural diagram of an electrical desiliconization device of the present invention. The water inlet a, the water outlet b, the sewage outlet c, the electrode plate anode interface e and the electrode plate cathode interface.
FIG. 4 is a basic process flow diagram of the white carbon black produced by the carbonization method in the prior art.
Detailed Description
The method for treating wastewater from the production of white carbon black by carbonization according to the present invention is described in detail below.
In the prior art, the common precipitated white carbon black wastewater treatment usually adopts pure chemical silicon removal modes such as aluminum salt (PAC flocculant + PAM coagulant aid) and the like or adopts an electrochemical device to remove silicon. Although the chemical silicon removal mode has a certain removal effect on the colloidal silicon, the removal efficiency on the soluble silicon is extremely low, so that a large amount of soluble silicon enters a subsequent ultrafiltration membrane and a reverse osmosis membrane, and silica scale is formed on the surface of the membrane after several hours to pollute the plugging membrane. In the current technology, the best method for cleaning silicon dioxide pollution is to clean with hydrofluoric acid, but the use of hydrofluoric acid cleaning can cause irreparable damage to the film, so once the film forms a silicon plug, the film cannot be cleaned at all in actual operation, only a new film can be replaced, and the cost is too high due to the use of a large amount of chemical silicon removal agents, and enterprises cannot bear high operating cost. While the electrochemical silicon removal can well remove soluble silicon and ensure that a subsequent reverse osmosis membrane is not blocked, the mixed salt solution of sodium carbonate and sodium bicarbonate in the wastewater cannot be separated, and only the common precipitated white carbon black wastewater produced by taking inorganic acid as a raw material can be treated. Therefore, no method for treating the white carbon black wastewater by the carbonization method exists in the prior art, so that enterprises producing the white carbon black by the carbonization method cannot realize zero discharge of wastewater treatment. Therefore, the invention provides a method for treating wastewater produced by producing white carbon black by a carbonization method, which comprises the following steps:
1) Cooling the wastewater to be treated, and then carrying out electrolytic desiliconization treatment;
2) Carrying out ultrafiltration treatment on the wastewater subjected to electrolytic desiliconization in the step 1) to provide ultrafiltration treatment water;
3) Performing reverse osmosis treatment on the ultrafiltration treatment water provided by the step 2) to provide first produced water and first concentrated water;
4) Carrying out nanofiltration membrane treatment on the first concentrated water provided by the step 3) to provide second produced water and second concentrated water;
5) Evaporating the second produced water provided in step 4) to provide sodium bicarbonate;
6) Evaporating the second concentrated water provided by the step 5) to provide sodium carbonate.
In the method for treating wastewater produced by the white carbon black production by the carbonization method, step 1) is to perform electrolytic desiliconization treatment after the wastewater to be treated is cooled. Wherein the wastewater to be treated is wastewater produced by the carbonization method of white carbon black.
In step 1), in order to improve the effect of the electrical desiliconization treatment, in a preferred embodiment of the present invention, before the electrical desiliconization treatment, only the wastewater of the carbon white carbon black is required to be cooled. Different from the prior art for treating the common precipitation method white carbon black wastewater, the step of sending the cooled wastewater to a precipitation wastewater tank for natural precipitation and adding alkali into the naturally precipitated wastewater for neutralization is omitted for treating the carbonization method white carbon black wastewater. The cooling treatment may be performed in a cooling tower, for example.
Specifically, production wastewater containing sodium bicarbonate and sodium carbonate and generated in the white carbon black production process by a carbonization method enters a workshop wastewater tank, the temperature of the wastewater is usually about 70 ℃, the wastewater is conveyed to a wastewater cooling tower by a hot water pump for cooling treatment, the temperature of the wastewater is reduced to below 40 ℃ and then enters a regulating tank for caching, and then the wastewater cooled in the regulating tank is conveyed to an electric desiliconization device by the wastewater pump.
In the step 1), electrolytic silicon removal can be carried out in an electric silicon removal device, for example, wherein the electric silicon removal device comprises a water inlet, a cavity and a water outlet which are sequentially communicated with each other in a fluid manner; a sewage draining outlet is formed in the bottom of the cavity; an anode plate and a cathode plate are arranged in the cavity; the device also comprises an electrode plate anode interface connected with the anode plate and an electrode plate cathode interface connected with the cathode plate.
The invention utilizes the existing electrolytic chemical equipment and flocculation technology to remove colloidal silica and soluble silicon (short for electric desiliconization) in the white carbon black wastewater by the carbonization method. The electric desiliconization device (see figure 3) is desiliconization equipment which is drawn up according to the electrochemical electrolysis principle, and the working principle is as follows: the metal is used as an electrode, waste water to be treated is electrolyzed from the electrode plates, chemical substances generated by the metal electrode during electrolysis and colloidal silicon and soluble silicon in the white carbon black waste water are subjected to a series of complex electrochemical reactions, or are removed by oxidation, or are separated out by dissociation, or are taken out of a water body by secondary gas, or are subjected to reduction reaction and the like, and finally the removal of the colloidal silicon and the soluble silicon is realized.
In a specific implementation scenario, a specific flow of the electrical desilication process is briefly described as follows (see fig. 2): under the condition of certain current and voltage, fe dissolved out of the metal anode 2+ 、Al 3+ (the preferred use of Fe dissolution in the present invention 2+ Electrochemical device) plasma is hydrolyzed in water to generate flocculation, and H is generated by the anode and the cathode 2 And O 2 The air bubbles in the air flow are equal to each other, so that good air floating effect is generated, and O is generated 2 The oxidation effect is also realized on the colloidal silica and soluble silica in the white carbon black wastewater and other pollution to-be-removed substances. Colloidal silica and soluble silica in the white carbon black wastewater treated by the electrolytic chemical flocculation equipment are changed into flocs such as metal oxides, hydroxides and the like, so that the flocs are removed by a precipitation mode.
In order to more conveniently and effectively remove flocs such as metal oxides and hydroxides formed in the electrical desiliconization treatment, according to the characteristics of the precipitated silica wastewater by the carbonization method, in a preferred embodiment of the present invention, a desiliconization agent is added to the wastewater after electrical desiliconization after the electrical desiliconization treatment and before the ultrafiltration treatment.
Specifically, flocs such as metal oxides, hydroxides and the like formed by the electric desiliconization treatment are matched with a small amount of desiliconization agent, so that the specific surface area of the particles of the flocs is increased, the activity is improved, the stability is good, and the precipitation effect is better.
In some embodiments, the silicon removing agent may be selected from, for example, LMSI-23 manufactured by shanghai li mai environmental protection equipment ltd.
In some embodiments, the silicon removal agent is used in an amount of 0.15 to 0.2kg/t water. Namely, the dosage of the silicon removing agent in 1 ton of water is 0.15-0.2 kg.
The invention separates flocculate from brine through ultrafiltration treatment to obtain ultrafiltration treated water. After the white carbon black wastewater is electrically desiliconized, flocculated and precipitated, the rest suspended matters containing silicide are left, and then most of silicide in the water can be removed by a subsequent immersed ultrafiltration membrane system. The immersed ultrafiltration membrane system is membrane separation equipment adopting the immersed ultrafiltration membrane, can be directly immersed in a water tank, and can be flushed by air disturbance, so that the ultrafiltration membrane can still stably run when the concentration of suspended matters in the white carbon black wastewater reaches 1-2%. The submerged ultrafiltration system may be, for example, a system of application No. 201720311859.3.
In order to fully recover and treat the white carbon black wastewater, in a preferred embodiment of the invention, the ultrafiltration flocculate is sent to a sludge tank, and dehydrated sludge is separated by solid-liquid separation. Specifically, after the wastewater subjected to electric desiliconization is added with a desiliconization agent to flocculate silicon in the wastewater, the wastewater enters an immersed ultrafiltration membrane system to separate flocculate from water, the separated flocculate (sludge) is discharged into a sludge tank, and the sludge is subjected to solid-liquid separation and dehydration to separate dehydrated sludge with low water content and is pulled away for subsequent treatment.
In the method for treating wastewater produced in the production of white carbon black by the carbonization method, step 3) is to perform reverse osmosis treatment on the ultrafiltration treatment water provided in step 2) to obtain first produced water and second concentrated water.
In the step 3), the ultrafiltration treatment water is pumped into a reverse osmosis membrane system for concentration under the pressure of 6MPa to 9MPa, 6MPa to 7MPa, 7MPa to 8MPa, 8MPa to 9MPa and the like.
In the step 3), in order to ensure that the reverse osmosis membrane operates stably, the reverse osmosis treatment is carried out after the high-silicon scale inhibitor and the reducing agent are added into the ultrafiltration treatment water provided in the step 2).
In a preferred embodiment of the invention, a high silica scale inhibitor and a reducing agent are added to the ultrafiltration product water prior to the reverse osmosis treatment. The high-silicon scale inhibitor and the reducing agent are optimized according to the characteristics of the white carbon black wastewater produced by the carbonization method, and the optimized high-silicon scale inhibitor is more favorable for controlling scales and deposits in a reverse osmosis membrane concentration system and reducing particle blockage; the reducing agent is preferably used to protect the reverse osmosis membrane from oxidation. It is to be noted that the adding positions and adding amounts of the silicon remover, the high-silicon scale remover and the reducing agent are greatly improved compared with the prior art for treating the common precipitated white carbon black, the silicon remover and the coagulant aid are added after the electrical silicon removal is carried out on the common precipitated white carbon black, and only the high-silicon scale inhibitor is added after the immersed ultrafiltration membrane is added, which are all within the protection scope of the invention. The pore size of the selected ultrafiltration membrane can be 0.01-0.1 μm, 0.01-0.05 μm, or 0.05-0.1 μm, etc.
In some embodiments, the high silica scale inhibitor may be, for example, LMZG-5SI, manufactured by Shanghai Limai environmental protection Equipment, inc. The dosage of the high-silicon scale inhibitor is 0.0015-0.0025 kg/t water. Namely, the dosage of the high-silicon scale inhibitor in 1 ton of water is 0.0015-0.0025 kg.
In some embodiments, the reducing agent may be, for example, sodium bisulfite. The dosage of the reducing agent is 0.004-0.005 kg/t. Namely, the dosage of the reducing agent in 1 ton of water is 0.004-0.005 kg.
In some embodiments, the concentration of the sodium bicarbonate and sodium carbonate mixed solution after concentration by the reverse osmosis membrane is 7-8%.
In some embodiments, the first produced water is reused for production in step 3).
In the method for treating wastewater produced in the production of white carbon black by the carbonization method, step 4) is to perform nanofiltration membrane treatment on the first concentrated water provided in step 3) to provide second produced water and second concentrated water.
After the nanofiltration membrane treatment, the second concentrated water comprises a sodium carbonate solution, and the sodium carbonate solution contains a small amount of sodium bicarbonate. In some embodiments, the concentration of sodium bicarbonate can be, for example, 50 to 85g/l, 50 to 60g/l, 60 to 70g/l, or 70 to 85g/l, etc. The concentration of sodium carbonate can be 80-100 g/l, 80-90 g/l, or 90-100 g/l.
In some embodiments, a small amount of sodium bicarbonate in the second concentrated water can be converted to sodium carbonate by adjusting the pH with a base.
The second water product comprises sodium bicarbonate solution. In some embodiments, the concentration of sodium bicarbonate is 50-85 g/l, 50-60 g/l, 60-70 g/l, or 70-85 g/l, etc. The sodium carbonate solution contains a small amount of sodium carbonate, and the concentration of sodium carbonate may be, for example, 0.2 to 0.4g/l, 0.2 to 0.3g/l, 0.3 to 0.4g/l, or the like.
In some embodiments, the nanofiltration membrane process is a separation performed in a nanofiltration membrane system. The aperture of the nanofiltration membrane is 0.01-0.1 nm.
In the method for treating wastewater produced in the production of white carbon black by the carbonization method, the second produced water provided in the step 4) is evaporated in the step 5) to provide sodium bicarbonate. The obtained sodium bicarbonate (baking soda) is more than industrial I-class qualified product.
Specifically, the second product water is pumped into an evaporation system for evaporation treatment. The temperature of evaporation is less than or equal to 65 ℃.
And 5) obtaining evaporation condensate water after evaporation treatment in the step 5), and reusing the evaporation condensate water for production.
In the method for treating wastewater produced in the production of white carbon black by the carbonization method, step 6) is to evaporate the second concentrated water provided in step 5) to provide sodium carbonate. The obtained sodium carbonate (soda ash) is more than industrial I-class qualified product.
Specifically, the second concentrated water is pumped into an evaporation system for evaporation treatment. The temperature of evaporation can be 100-120 ℃, 100-110 ℃, or 110-120 ℃ and the like.
Evaporating condensed water obtained after evaporation treatment in the step 6), and reusing the evaporated condensed water for production.
In summary, since the production of white carbon black by the carbonization method is a special production method of precipitated white carbon black, unlike the common precipitated white carbon black, the production wastewater of the carbonized white carbon black carries not a single sodium salt but a mixed salt of sodium bicarbonate and sodium carbonate, and the mixed salt is not only required to be separated from the wastewater, but also to be thoroughly separated to prepare two products. While the waste water produced by the common precipitation method of white carbon black only contains single sodium salt, such as: or sodium sulfate, or sodium chloride, or sodium nitrate. Therefore, the method for treating the wastewater generated in the production of the white carbon black by the carbonization method cannot be directly adopted when the wastewater is treated. Therefore, the invention discloses a method for treating wastewater produced by producing carbon white by a carbonization method, which comprises the steps of cooling the wastewater produced by producing the carbon white by the carbonization method, sending the wastewater into a regulating tank for caching, and then carrying out silicon removal treatment; carrying out ultrafiltration treatment on the wastewater subjected to electric desiliconization through an immersed ultrafiltration membrane to obtain ultrafiltration treated water; performing reverse osmosis treatment on the ultrafiltration treatment water to obtain first produced water (clear water) and first concentrated water; carrying out nanofiltration membrane treatment on the first concentrated water, and separating by using a nanofiltration membrane to respectively obtain a second produced water and a second concentrated water; and evaporating the second produced water to obtain sodium bicarbonate (baking soda), and evaporating the second concentrated water to obtain sodium carbonate (soda ash).
At present, the method for removing soluble silicon in the white carbon black wastewater by using electric desiliconization, matching with ultrafiltration treatment and reverse osmosis membrane concentration, and then separating and treating the white carbon black wastewater by using a nanofiltration membrane belongs to the technical blank. Experiments prove that compared with the existing precipitated white carbon black wastewater treatment technology, the process method disclosed by the invention can be used for more effectively removing soluble silicon in the white carbon black wastewater by a carbonization method, so that the service lives of a subsequent ultrafiltration membrane and a reverse osmosis membrane are longer; and meanwhile, the nanofiltration membrane is used for separating the sodium bicarbonate and the sodium carbonate, so that the separation efficiency is high, the sodium bicarbonate and the sodium carbonate solution in the white carbon black production wastewater produced by the carbonization method can be effectively separated, and the sodium bicarbonate and the soda ash products are produced by utilizing an evaporation system, so that the economy is good. The method greatly reduces the treatment cost of the white carbon black wastewater by the carbonization method, and really realizes zero discharge of the white carbon black production wastewater by the carbonization method.
The following examples are provided to further illustrate the advantageous effects of the present invention.
In order to make the purpose, technical solutions and advantageous technical effects of the present invention clearer, the present invention is described in further detail below with reference to examples. However, it should be understood that the embodiments of the present invention are only for explaining the present invention and are not for limiting the present invention, and the embodiments of the present invention are not limited to the embodiments given in the specification. The examples were prepared under conventional conditions or conditions recommended by the material suppliers without specifying specific experimental conditions or operating conditions.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that a combinational connection relationship between one or more devices/apparatuses mentioned in the present invention does not exclude that other devices/apparatuses may also be present before or after the combinational device/apparatus or that other devices/apparatuses may also be interposed between the two devices/apparatuses explicitly mentioned, unless otherwise stated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Example 1
The treatment process for treating the white carbon black wastewater by using the carbonization method of the invention cools the white carbon black wastewater from the workshop wastewater tank by using the wastewater cooling tower, sends the cooled wastewater to the regulating tank for caching, and then carries out electric desiliconization by using the desiliconization device. Adding a desiliconization agent (LMSI-23) after electric desiliconization, and feeding the mixture through an immersed ultrafiltration membrane systemPerforming ultrafiltration treatment, adding high silicon scale inhibitor (LMZG-5 SI) and reducing agent (NaHSO) into the ultrafiltration treatment water 3 ) And then reverse osmosis treatment is carried out through a reverse osmosis membrane system to obtain first produced water and first concentrated water. And (2) sending the first concentrated water to a nanofiltration membrane system for separation, respectively obtaining second produced water (sodium bicarbonate solution) and second concentrated water (sodium carbonate solution containing a certain amount of sodium bicarbonate) through the separation of the nanofiltration membrane system, sending the second produced water to an evaporation system 1, sending the second concentrated water to an evaporation system 2 for evaporation treatment, controlling the evaporation temperature of the evaporation system 1 to be less than or equal to 65 ℃, and controlling the evaporation temperature of the evaporation system 2 to be 100-120 ℃ to obtain sodium bicarbonate (baking soda) and sodium carbonate (soda). The evaporated condensed water in the evaporation system 1 and the evaporation system 2 and the first produced water (clean water) are sent to a clean water tank for the production system to use. It should be noted that in example 1, firstly, a silicon removal agent is added before the immersed ultrafiltration membrane system, 3 agents are required to be added before the reverse osmosis membrane by simultaneously adding a reducing agent and a high-silicon scale inhibitor, and the addition amounts of the three agents are detailed in tables 5 and 6; in order to further separate sodium bicarbonate and sodium carbonate, a nanofiltration membrane separation system is added behind a reverse osmosis membrane system, which is essentially different from the conventional white carbon black wastewater treatment technology.
Comparative example 1
The conventional white carbon black wastewater treatment process is utilized, the carbonization white carbon black wastewater from a workshop wastewater tank is cooled by a wastewater cooling tower, the cooled wastewater is sent to a regulating tank, the pH value is regulated to be neutral by alkali (generally 30 percent NaOH) during the cooling process and then is stored, and then the electric desiliconization treatment is carried out by an electric desiliconization device. Adding a certain amount of desiliconization agent (containing FeCl) after the electric desiliconization 3 Compound type) and coagulant aid (PAM), carrying out ultrafiltration treatment by an immersed ultrafiltration membrane system, adding a high-silicon scale inhibitor (organic phosphate) after the water is subjected to ultrafiltration treatment, and carrying out reverse osmosis treatment by a reverse osmosis membrane system to obtain 'produced water' and 'concentrated water' (mixed solution of sodium carbonate and sodium bicarbonate). And (3) delivering the concentrated water to an evaporation system for evaporation treatment, and controlling the evaporation temperature to be 100-120 ℃ to obtain a sodium carbonate product. Sending the evaporated condensed water of the evaporation system and the 'produced water' (clear water) to the clear waterA water tank for use by the production system. It should be noted that in comparative example 1 (prior art), alkali is added for neutralization before electric desilication, while desilication agent and coagulant aid are added after the electric desilication device, and high-silicon scale inhibitor is added after the submerged ultrafiltration membrane (before the reverse osmosis membrane), and 4 agents (alkali, desilication agent, coagulant aid and high-silicon scale inhibitor) are added in the prior art, and the addition amounts of the four agents are shown in tables 5-1 and 6-1.
Embodiment 1 is a process technology for treating wastewater of carbon white by using an electric desiliconization device to remove silicon, using an ultrafiltration membrane system to perform ultrafiltration treatment, and using a reverse osmosis membrane system to concentrate and a nanofiltration membrane system to separate. The difference between example 1 and comparative example 1 is: firstly, the part of the invention (example 1) where alkali, a silicon removing agent, a high-silicon scale remover, a coagulant aid and a reducing agent are added is greatly improved compared with the prior art (comparative example 1) for treating the common white carbon black. The common white carbon black is treated by adding alkali for neutralization before electric desiliconization, adding a desiliconization agent and a coagulant aid after the electric desiliconization (before an ultrafiltration membrane system), adding a high-silicon scale inhibitor after the ultrafiltration membrane system, and adding 4 agents in total, while the method only needs to add 3 agents (the desiliconization agent, the high-silicon scale inhibitor and the reducing agent); secondly, the first concentrated water obtained after reverse osmosis treatment is sent to a nanofiltration membrane system, a nanofiltration membrane system is used for separating to respectively obtain second produced water (sodium bicarbonate solution) and second concentrated water (sodium carbonate solution containing a small amount of sodium bicarbonate), the content of sodium bicarbonate and the content of sodium carbonate in the second concentrated water are shown in a table 4-1, and then the second produced water and the second concentrated water are respectively sent to an evaporation system 1 and an evaporation system 2 to obtain sodium bicarbonate (baking soda) and sodium carbonate (soda ash). When white carbon black wastewater is treated by the traditional technology, as the wastewater only contains single sodium salt (sodium sulfate, sodium chloride or sodium nitrate and the like), concentrated water obtained after a reverse osmosis membrane system is concentrated is directly sent to be evaporated to obtain sodium salt (sodium sulfate, sodium chloride or sodium nitrate) products.
Table 2 is a comparison of the silicon content data for water before entering the reverse osmosis membrane module for example 1 and comparative example 1; table 3 shows the operating data of the reverse osmosis membrane system of comparative example 1; table 4 shows the operating data for the reverse osmosis membrane system of example 1; table 4-1 shows the nanofiltration membrane system operation data in example 1.
Table 2 comparison of silicon content data for water before entering reverse osmosis membrane module for example 1 and comparative example 1
Table 3 operating data for the reverse osmosis membrane system of comparative example 1
Table 4 operating data for the reverse osmosis membrane system of example 1
Table 4-1 nanofiltration membrane system operating data in example 1
| First concentrated water of reverse osmosis system | Second produced water of nanofiltration membrane system | Second concentrated water of nanofiltration membrane system | |
| Sodium carbonate concentration g/l | 42.14 | 0.3 | 85 |
| Sodium bicarbonate concentration g/l | 51.67 | 51.67 | 51.67 |
TABLE 5 amount of silicon remover used in example 1
TABLE 5-1 dosage of alkali, silicon remover, coagulant aid in comparative example 1
TABLE 6 amount of reducing agent, high silica scale inhibitor used in example 1
TABLE 6-1 amount of the high silica scale inhibitor used in comparative example 1
As can be seen from Table 2, the electrochemical silicon removal method in the prior art for treating the precipitated silica wastewater can only remove the silicon content in the wastewater from 330mg/L to 55mg/L or less, and although the service life of the membrane can be prolonged, the membrane still has silicon blockage caused by long-time operation, and the cleaning frequency of the membrane is increased. As shown in Table 3, the concentrated brine content of the reverse osmosis membrane after electro-desiliconization by adopting the prior art can only reach below 6.0 percent of the highest content, the flow of the clear water and the flow of the concentrated brine are gradually reduced along with the time in the operation process, and the pressure difference between the inlet and the outlet of the reverse osmosis membrane is increased. This shows that the reverse osmosis membrane is more and more seriously blocked along with the progress of time, and shows that the prior art for treating white carbon black by a common precipitation method can only treat single sodium salt and is not suitable for treating sodium salt of a sodium bicarbonate and sodium carbonate mixed system.
The conventional technology for treating the white carbon black by the common precipitation method has the following defects: 1. the traditional treatment mode is customized according to the characteristics of the waste water produced by the common white carbon black, and the pH value of the waste water is only about 4.5, so that the waste water can be adjusted to be neutral by adding alkali. The precipitation of the silicon salt flocculate can occur in the process of regulating the pH value, so that a coagulant aid needs to be added in addition to the silicon agent before the silicon salt flocculate enters an ultrafiltration membrane system, the ultrafiltration effect can be improved, and the dosage of the medicament and the production cost are increased; 2. when the conventional treatment mode is used for treating the common white carbon black wastewater, as the wastewater only contains single sodium salt (sodium sulfate, sodium chloride or sodium nitrate and the like), concentrated water obtained after the reverse osmosis membrane system is concentrated is directly sent to be evaporated to obtain a single sodium salt product, such as: sodium sulfate, sodium chloride, sodium nitrate, etc., and sodium bicarbonate and sodium carbonate in the mixed salt system cannot be separated.
The invention utilizes the electric desiliconization device to remove soluble silicon in the wastewater, combines ultrafiltration treatment and reverse osmosis membrane concentration, and utilizes a nanofiltration membrane separation method to treat the white carbon black wastewater by the method, so that the content of the soluble silicon which is difficult to remove in the production wastewater can be economically removed from 330mg/L to below 20mg/L (see table 2), and the sodium bicarbonate and the sodium carbonate mixed salt are successfully separated. Practice proves that no silicon blockage occurs no matter the content of silicon in the ultrafiltration membrane, the reverse osmosis membrane or the nanofiltration membrane is below 20 mg/L. And (2) concentrating the wastewater after silicon removal in a reverse osmosis membrane system with a relatively mature technology to obtain first produced water (clear water) and concentrated water 1 (a sodium bicarbonate and sodium carbonate mixed solution), further separating second produced water (a sodium bicarbonate solution) and second concentrated water (a sodium carbonate solution containing a small amount of sodium bicarbonate) from the first concentrated water by using a nanofiltration membrane system, and evaporating the second produced water (the sodium bicarbonate solution) and the second concentrated water (the sodium carbonate solution containing a small amount of sodium bicarbonate) respectively to obtain sodium bicarbonate (baking soda) and sodium carbonate (soda ash) products as shown in Table 4-1. As shown in table 4, when the reverse osmosis membrane system is used for removing silicon by using the electric silicon removal device, the salt content of the concentrated water concentrated by the reverse osmosis membrane system can reach 8%, the flow of the clear water and the concentrated water in the operation process of the reverse osmosis membrane is not obviously changed along with the time, the pressure difference between the inlet and the outlet of the reverse osmosis membrane is not changed, the reverse osmosis membrane system can still normally operate after 480 hours of continuous operation, and the membrane blockage phenomenon cannot be generated. As shown in table 4-1, the wastewater after silicon removal and concentration is a mixed solution containing high-concentration sodium bicarbonate and sodium carbonate, the sodium bicarbonate solution and the sodium carbonate solution can be successfully separated by using a nanofiltration membrane system, and the sodium bicarbonate solution (product water 2) enters an evaporation system 1 to produce a sodium bicarbonate (baking soda) product; sodium carbonate solution (second concentrated water) containing a small amount of sodium bicarbonate is added with sodium hydroxide to adjust the pH value and then enters an evaporation system 2 to produce a sodium carbonate (soda ash) product. The invention adopts an electric desiliconization method and a method for separating mixed salt by a nanofiltration membrane system, which can realize the aim of removing silicon from the white carbon black wastewater by a carbonization method through consuming electricity and a small amount of electrodes, the wastewater after silicon removal can be separated into mixed sodium salts (sodium bicarbonate and sodium carbonate) by the nanofiltration membrane system after ultrafiltration concentration, the operation cost is relatively low, the electricity and electrode cost consumed by electric desiliconization is 1.6 yuan/ton of wastewater, the consumption cost of the nanofiltration membrane system (mainly replacing the nanofiltration membrane) is 1.1 yuan/t, and the two increased costs are within the acceptable range of enterprises. The technology has good silicon removal effect, so that the service life of the ultrafiltration membrane and the reverse osmosis membrane is longer, and meanwhile, the nanofiltration membrane is used for separating sodium bicarbonate and sodium carbonate mixed salt, so that the economy is good, the separation effect of the mixed salt is improved, and the treatment cost of the white carbon black wastewater by the carbonization method is greatly reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
Claims (10)
1. A treatment method of wastewater produced by carbonizing white carbon black comprises the following steps:
1) Cooling the wastewater to be treated, and then carrying out electrolytic desiliconization treatment;
2) Carrying out ultrafiltration treatment on the wastewater subjected to electrolytic desiliconization in the step 1) to provide ultrafiltration treatment water;
3) Subjecting the ultrafiltration treatment water provided in the step 2) to reverse osmosis treatment to provide first produced water and first concentrated water;
4) Carrying out nanofiltration membrane treatment on the first concentrated water provided by the step 3) to provide second produced water and second concentrated water;
5) Evaporating the second produced water provided in step 4) to provide sodium bicarbonate;
6) Evaporating the second concentrated water provided by the step 5) to provide sodium carbonate.
2. The method for treating wastewater produced by producing white carbon black through carbonization according to claim 1, wherein the wastewater to be treated in the step 1) is electrolyzed under the current of 20-40A and the voltage of 15-40V, and metal ions dissolved out from the metal anode are hydrolyzed in water to generate flocculation; the anode produces oxygen and the cathode produces hydrogen, which after electrolysis, colloidal and soluble silicon become flocs, which are oxides and hydroxides of metals.
3. The method for treating wastewater produced in the production of white carbon black by carbonization according to claim 1, wherein in the step 2), the wastewater after the electrolytic silicon removal in the step 1) is added with a silicon removal agent and then is subjected to ultrafiltration treatment; preferably, the dosage of the silicon removing agent is 0.15-0.2 kg/t water.
4. The method for treating wastewater produced by producing fumed silica according to claim 1, wherein flocs are obtained after the ultrafiltration treatment in step 2), and the flocs are subjected to solid-liquid separation to obtain dewatered sludge.
5. The method for treating wastewater produced by producing white carbon black through carbonization according to claim 1, wherein in the step 3), the high silica scale inhibitor and the reducing agent are added into the ultrafiltration treatment water provided in the step 2) for reverse osmosis treatment; preferably, the dosage of the high-silicon scale inhibitor is 0.0015 to 0.0025kg/t water; the reducing agent is selected from sodium bisulfite; the dosage of the reducing agent is 0.004-0.005 kg/t.
6. The method for treating wastewater from production of carbon white according to claim 1, wherein the first produced water obtained in step 3) is reused for production.
7. The method for treating wastewater produced by producing carbon white according to claim 1, wherein evaporation condensate water is obtained after evaporation treatment in step 4) and step 5), and the evaporation condensate water is reused for production.
8. The method for treating wastewater from the production of fumed silica according to claim 1, wherein the second concentrated water comprises a sodium carbonate solution, and the sodium carbonate solution comprises sodium bicarbonate.
9. The method for treating wastewater produced by producing carbon white according to claim 8, wherein the content of the sodium bicarbonate is 50-85 g/l; the content of the sodium carbonate is 80-100 g/l.
10. The method for treating wastewater from production of carbon white according to claim 1, wherein the second production water comprises a sodium bicarbonate solution; preferably, the concentration of the sodium bicarbonate is 50-85 g/l; the sodium carbonate solution contains sodium carbonate, and the concentration of the sodium carbonate is 0.2-0.4 g/l.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005288219A (en) * | 2004-03-31 | 2005-10-20 | Miura Co Ltd | Water supply system |
| CN103449571A (en) * | 2013-08-22 | 2013-12-18 | 煤炭科学研究总院杭州环保研究院 | Method and device for processing pit water |
| US20160244348A1 (en) * | 2013-10-28 | 2016-08-25 | Crs Industrial Water Treatment Systems Pty Ltd | A method for treating alkaline brines |
| CN110255758A (en) * | 2019-06-05 | 2019-09-20 | 厦门嘉戎技术股份有限公司 | A kind of high alkalinity method for treating garbage percolation liquid and device |
| CN111807596A (en) * | 2020-08-27 | 2020-10-23 | 潍坊美好生活环保科技有限公司 | Process method for treating precipitated white carbon black wastewater |
| CN111925061A (en) * | 2020-08-13 | 2020-11-13 | 福建思科硅材料有限公司 | Recycling treatment process for white carbon black production wastewater |
| CN112010484A (en) * | 2020-08-11 | 2020-12-01 | 内蒙古久科康瑞环保科技有限公司 | Mine water treatment system with high salinity and high alkalinity and treatment method thereof |
| CN112142249A (en) * | 2020-09-30 | 2020-12-29 | 煤科集团杭州环保研究院有限公司 | SO (SO)4·HCO3Method and system for treating and recycling-Na-type high-salt mine water |
| CN113149317A (en) * | 2021-04-23 | 2021-07-23 | 上海晶宇环境工程股份有限公司 | Industrial wastewater treatment method |
| CN214990901U (en) * | 2020-08-27 | 2021-12-03 | 江西黑猫炭黑股份有限公司 | Process system for treating precipitated white carbon black wastewater |
| CN215480149U (en) * | 2021-09-10 | 2022-01-11 | 安徽科博瑞环境科技有限公司 | Receive filter membrane drinking water processing system |
-
2022
- 2022-04-08 CN CN202210370133.2A patent/CN115448512A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005288219A (en) * | 2004-03-31 | 2005-10-20 | Miura Co Ltd | Water supply system |
| CN103449571A (en) * | 2013-08-22 | 2013-12-18 | 煤炭科学研究总院杭州环保研究院 | Method and device for processing pit water |
| US20160244348A1 (en) * | 2013-10-28 | 2016-08-25 | Crs Industrial Water Treatment Systems Pty Ltd | A method for treating alkaline brines |
| CN110255758A (en) * | 2019-06-05 | 2019-09-20 | 厦门嘉戎技术股份有限公司 | A kind of high alkalinity method for treating garbage percolation liquid and device |
| CN112010484A (en) * | 2020-08-11 | 2020-12-01 | 内蒙古久科康瑞环保科技有限公司 | Mine water treatment system with high salinity and high alkalinity and treatment method thereof |
| CN111925061A (en) * | 2020-08-13 | 2020-11-13 | 福建思科硅材料有限公司 | Recycling treatment process for white carbon black production wastewater |
| CN111807596A (en) * | 2020-08-27 | 2020-10-23 | 潍坊美好生活环保科技有限公司 | Process method for treating precipitated white carbon black wastewater |
| CN214990901U (en) * | 2020-08-27 | 2021-12-03 | 江西黑猫炭黑股份有限公司 | Process system for treating precipitated white carbon black wastewater |
| CN112142249A (en) * | 2020-09-30 | 2020-12-29 | 煤科集团杭州环保研究院有限公司 | SO (SO)4·HCO3Method and system for treating and recycling-Na-type high-salt mine water |
| CN113149317A (en) * | 2021-04-23 | 2021-07-23 | 上海晶宇环境工程股份有限公司 | Industrial wastewater treatment method |
| CN215480149U (en) * | 2021-09-10 | 2022-01-11 | 安徽科博瑞环境科技有限公司 | Receive filter membrane drinking water processing system |
Non-Patent Citations (1)
| Title |
|---|
| 朱灵峰编著: "《水与废水处理新技术》", 31 August 2007, 西安地图出版社, pages: 256 * |
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