CN105502307B - The method and special purpose device of waste acid concentration defluorinating chlorine - Google Patents
The method and special purpose device of waste acid concentration defluorinating chlorine Download PDFInfo
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- CN105502307B CN105502307B CN201510982827.1A CN201510982827A CN105502307B CN 105502307 B CN105502307 B CN 105502307B CN 201510982827 A CN201510982827 A CN 201510982827A CN 105502307 B CN105502307 B CN 105502307B
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- acid
- chlorine
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- waste acid
- fluorine
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- 239000002253 acid Substances 0.000 title claims abstract description 91
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000460 chlorine Substances 0.000 title claims abstract description 60
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001704 evaporation Methods 0.000 claims abstract description 38
- 230000008020 evaporation Effects 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004094 preconcentration Methods 0.000 claims abstract description 25
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims 1
- 229910052602 gypsum Inorganic materials 0.000 abstract description 4
- 239000010440 gypsum Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 230000008676 import Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 101100290713 Caenorhabditis elegans mef-2 gene Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UXNBTDLSBQFMEH-UHFFFAOYSA-N [Cu].[Zn].[Pb] Chemical compound [Cu].[Zn].[Pb] UXNBTDLSBQFMEH-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a kind of method of waste acid concentration defluorinating chlorine and special purpose device, the waste acid after vulcanizing treatment is concentrated by multiple-effect evaporation, by waste acid more than 90% moisture evaporation；The temperature that multiple-effect evaporation control the concentration of waste acid when concentrating is 25% 40%, control waste acid is 105 DEG C 110 DEG C, fluorine chlorine is remained in waste acid, obtains pre-concentration sour；The temperature of pre-concentration acid is maintained at 125 DEG C 145 DEG C in reboiler using initial steam, then pre-concentration acid enters defluorinate chlorine tower, in defluorinate chlorine tower, after the fluorine chlorine in sulfuric acid separates sulfuric acid through multistage column plate, is taken out of with water vapour from tower top；Partial cleansing acid is taken out in bottom of towe, Partial cleansing acid still returns to reboiler.The present invention without gypsum tailings, can be greatly lowered energy resource consumption, plant investment save waste acid concentration defluorinating chlorine method and special purpose device.
Description
Technical field
The present invention relates to a kind of method of waste acid concentration defluorinating chlorine and special purpose device.
Background technology
The flue gas acid preparing process of copper-lead-zinc smelting produces the substantial amounts of waste acid containing heavy metal, and conventional processing method is vulcanization
Neutralize.Therefore, the substantial amounts of gypsum tailings containing heavy metal is produced, Sulphur ressource is not utilized.In addition, processing after waste water in contain
Calcium sodium ion, can not substantially return and use.In recent years, domestic relevant manufacturing enterprise was researching and developing waste acid " vulcanization+heat
Wind take off " technology.Because dilute sulfuric acid water content is high, the moisture in stripping diluted acid is with fluorine chlorine, it is necessary to substantial amounts of temperature
For 180 DEG C -200 DEG C of hot-air.So, the energy consumption of device is very high.Particularly defluorinate chlorine equipment size is huge, cost is high.And
And, air band after defluorinate chlorine acid amount is big, sulfuric acid concentration that is obtaining is low, tail gas treatment device investment is big.In addition, flue gas acid preparing mistake
The waste acid change in concentration that journey is produced is big, and hot blast stripping device adaptability is poor, operation stability is poor.
The content of the invention
It is an object of the invention to provide a kind of no gypsum tailings, energy resource consumption, plant investment province can be greatly lowered
Waste acid concentration defluorinating chlorine method and special purpose device.
The present invention technical solution be：
A kind of method of waste acid concentration defluorinating chlorine, it is characterized in that：Comprise the following steps：
（1）Waste acid after vulcanizing treatment is concentrated by multiple-effect evaporation, by waste acid more than 90% moisture evaporation；
Multiple-effect evaporation controls the concentration of waste acid to be 25%-40%, control the temperature of waste acid to be 105 DEG C -110 DEG C when concentrating, and fluorine chlorine is still protected
Hold in waste acid, obtain pre-concentration acid；The not fluorine-containing chlorine of water vapor condensation water that multiple-effect evaporation concentration is produced, can return to and use；
（2）The temperature of pre-concentration acid is maintained at 125 DEG C -145 DEG C in reboiler using initial steam, then pre-concentration acid
Into defluorinate chlorine tower, in defluorinate chlorine tower, after fluorine chlorine in sulfuric acid separates sulfuric acid through multistage column plate, with water vapour from tower top band
Go out；Partial cleansing acid is taken out in bottom of towe, Partial cleansing acid still returns to reboiler.
The water vapour of the fluorine-containing chlorine of defluorinate chlorine top of tower is condensed within the condenser, and condensate liquid then is delivered into the recovery of fluorine chlorine sets
It is standby.
The multiple-effect evaporation concentration is three-effect evaporation and condensation.
A kind of special purpose device of the method for waste acid concentration defluorinating chlorine, it is characterized in that：Including Multi-effect evaporation compression apparatus, multiple-effect
Defluorinate chlorine device is set after evaporation concentration device；The Multi-effect evaporation compression apparatus includes multi-stage evaporation unit, every grade of evaporation dress
Put and loop is composed in series by evaporator, heater, circulating pump, the gelled acid discharging opening of previous stage vaporising device is concatenated pump with after
One-level vaporising device acid inlet is connected, and the steam outlet of rear stage vaporising device is connected with previous stage heater；Afterbody
Defluorinate chlorine device is led in the pre-concentration acid outlet of vaporising device；The heater of afterbody vaporising device enters provided with saturated vapor
Mouthful；The defluorinate chlorine device includes preheater, and preheater is provided with the sour import of pre-concentration, the outlet of pre-concentration acid and defluorinate of preheater
Communicated in the middle part of chlorine tower, defluorinate chlorine tower bottom sets the indirect steam import being connected with reboiler, reboiler enters provided with saturated vapor
Mouthful, defluorinate chlorine tower bottom sets and sets tank connected with condensate on the sour first outlet of the purification being connected with reboiler, reboiler
Purification acid outlet, the purification acid outlet for condensing water pot is connected with preheater；Defluorinate chlorine tower bottom sets the sour second outlet of purification；It is de-
The steam outlet of fluorine chlorine top of tower is connected with condenser.
There is following reaction balance under certain temperature and certain sulfuric acid concentration in fluoride：
MeF2 + H2SO4 = 2HF + MeSO4
As a kind of middle strong acid, the degrees of dissociation of highly polar molecule HF in aqueous are not high, mainly with the fluorine of free state
The state for changing hydrogen molecule is present in the aqueous solution, and the presence of the concentrated sulfuric acid further suppress the electricity of fluorination hydrogen molecule in aqueous
From.But in the state of high temperature highly acidity, fluorination hydrogen molecule can escape whole solution system in the form of a vapor.This process meeting
The entropy of whole system is further increased, promotes whole reaction balance further to move right, reaches whole system defluorinate
Purpose.Similarly, hydrogen chloride will also be escaped in the same manner.
By small-scale test, demonstrate under conditions of relatively low acidity and temperature, hydrogen chloride and fluorination hydrogen molecule substantially without
Method is removed among solution system；When sulfuric acid concentration in solution and sufficiently high temperature, it is possible to by the overwhelming majority in solution
Hydrogen fluoride, hydrogen chloride removing.But, according to conventional evaporation and concentration, hydrogen fluoride, hydrogen chloride removal efficiency in sulfuric acid solution≤
80%, do not reach the technological requirement that acid making system is returned after waste acid purification.The indirect steam condensed water produced, fluorine chlorine are evaporated simultaneously
Content is higher, it is impossible to Returning utilization.The waste acid concentration defluorinating chlorine technique that we invent, in the waste acid pre-concentration stage, passes through control
The concentration and temperature of waste acid, make fluorine chlorine remain in waste acid during multiple-effect evaporation.The indirect steam condensed water that evaporation is produced is free of
Fluorine chlorine, can return and use.Pre-concentration acid enters back into special defluorinate chlorine device after heating.The device can realize that sulfuric acid is dense
Degree and the control and regulation of temperature, and multi-stage separation column plate is designed with, it can ensure that the hydrogen fluoride in sulfuric acid solution, hydrogen chloride take off
Except rate is more than 95%.
Waste acid is according to conventional process, after eliminating arsenic and heavy metal through over cure, clarification, filtering, into waste acid
Multi-effect evaporation compression apparatus.In Multi-effect evaporation compression apparatus, more than 90% moisture content is evaporated in waste acid.By controlling sulfuric acid
Concentration, temperature, the fluorine chlorine in acid is not separated out, the not fluorine-containing chlorine of indirect steam condensate liquid.Then, pre-concentration acid enters concentration and taken off
Fluorine chlorine device.In concentration defluorinating chlorine device, sulfuric acid concentration is further improved, temperature is further improved, by multi-stage separation tower
After plate, fluorine chlorine is set to be separated out from solution, and with water vapour（Indirect steam）Take system out of.Go out the purification of concentration defluorinating chlorine device
Acid, adds the absorption system that water enters sulphuric acid plant as relieving haperacidity, reclaims Sulphur ressource.Gone after water vapour containing fluorine chlorine is condensed
The retracting device of sodium fluoride, sodium chloride.
Advantages of the present invention：
1st, gypsum tailings is not produced, i.e., does not produce secondary pollution；
2nd, waste acid uses multiple-effect pre-concentration, is stripped of in waste acid more than 90% moisture, and this some vapor condensed water is not fluorine-containing
Chlorine, can return and use；
3rd, the sour defluorinate chlorine equipment of pre-concentration uses " reboiler+defluorinate chlorine tower ", and efficiency high, equipment size are small, reduced investment, with
Hot-air concentration defluorinating chlorine is compared, and energy consumption is greatly lowered；
4th, waste acid is after conventional vulcanization removing heavy metals and arsenic, after multiple-effect evaporation pre-concentration, reboiler defluorinate chlorine,
Acid making system can be added, Sulphur ressource is utilized.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is Multi-effect evaporation compression apparatus schematic diagram of the present invention.
Fig. 2 is defluorinate chlorine schematic device.
Embodiment
A kind of method of waste acid concentration defluorinating chlorine, comprises the following steps：
（1）Waste acid after vulcanizing treatment is concentrated by multiple-effect evaporation, by waste acid more than 90% moisture evaporation；
Multiple-effect evaporation controls the concentration of waste acid to be 25%-40%, control the temperature of waste acid to be 105 DEG C -110 DEG C when concentrating, and fluorine chlorine is still protected
Hold in waste acid, obtain pre-concentration acid；The not fluorine-containing chlorine of indirect steam condensed water produced is evaporated, can be returned as technique hot water
Use；The not fluorine-containing chlorine of water vapor condensation water that multiple-effect evaporation concentration is produced, can return to and use；
（2）The temperature of pre-concentration acid is maintained at 125 DEG C -145 DEG C in reboiler using initial steam, then pre-concentration acid
Into defluorinate chlorine tower, in defluorinate chlorine tower, after fluorine chlorine in sulfuric acid separates sulfuric acid through multistage column plate, with water vapour from tower top band
Go out；In defluorinate chlorine tower, after the fluorine chlorine in sulfuric acid separates sulfuric acid through multistage column plate, taken out of with water vapour from tower top.Will in bottom of towe
Partial cleansing acid takes out, and delivers to acid making system or take-away；Partial cleansing acid still returns to reboiler.Through this step, during pre-concentration is sour
Hydrogen fluoride, hydrogen chloride removal efficiency is more than 95%.Meanwhile, acid is dense further to be carried to 45%-60%.
The water vapour of the fluorine-containing chlorine of defluorinate chlorine top of tower is condensed within the condenser, and condensate liquid then is delivered into the recovery of fluorine chlorine sets
It is standby.
The multiple-effect evaporation concentration is three-effect evaporation and condensation.
A kind of special purpose device of the method for waste acid concentration defluorinating chlorine, including Multi-effect evaporation compression apparatus, multiple-effect evaporation concentration
Defluorinate chlorine device is set after device；The Multi-effect evaporation compression apparatus includes multi-stage evaporation unit, and every grade of vaporising device is by evaporating
Device 1, heater 2, circulating pump 3 are composed in series loop, and the gelled acid discharging opening of previous stage vaporising device is concatenated pump 4 and rear stage
Vaporising device acid inlet is connected, and the steam outlet 5 of rear stage vaporising device is connected with previous stage heater；Afterbody evaporates
Defluorinate chlorine device is led in the pre-concentration acid outlet of device；The heater of afterbody vaporising device is provided with saturated vapor import 6；Institute
Stating defluorinate chlorine device includes preheater 7, and preheater is provided with the sour import 8 of pre-concentration, pre-concentration acid outlet 9 and the defluorinate chlorine of preheater
The middle part of tower 10 is communicated, and defluorinate chlorine tower bottom sets the indirect steam import 12 being connected with reboiler 11, and reboiler is provided with saturation
Steam inlet 13, defluorinate chlorine tower bottom sets and set on the sour first outlet 14 of the purification being connected with reboiler, reboiler with condensing
The purification acid outlet 16 that water pot 15 is connected, the purification acid outlet 17 for condensing water pot is connected with preheater 7；Defluorinate chlorine tower bottom is set
The sour second outlet 18 of purification；The steam outlet 19 of defluorinate chlorine top of tower is connected with condenser 20.Condenser 20 is followed provided with industry
Water out 22 under water inlet 21, industrial cycle on ring.
Claims (3)
1. a kind of method of waste acid concentration defluorinating chlorine, it is characterized in that：Comprise the following steps：
(1) waste acid after vulcanizing treatment is concentrated by multiple-effect evaporation, by waste acid more than 90% moisture evaporation；Multiple-effect
The concentration that waste acid is controlled during evaporation and concentration is 25%-40%, controls the temperature of waste acid to be 105 DEG C -110 DEG C, fluorine chlorine is still kept
In waste acid, pre-concentration acid is obtained；The not fluorine-containing chlorine of water vapor condensation water that multiple-effect evaporation concentration is produced, can return to and use；
(2) temperature of pre-concentration acid is maintained at 125 DEG C -145 DEG C in reboiler using initial steam, then pre-concentration acid enters
Defluorinate chlorine tower, in defluorinate chlorine tower, after the fluorine chlorine in sulfuric acid separates sulfuric acid through multistage column plate, takes out of with water vapour from tower top；
Bottom of towe takes out Partial cleansing acid, and Partial cleansing acid still returns to reboiler.
2. the method for waste acid concentration defluorinating chlorine according to claim 1, it is characterized in that：The water of the fluorine-containing chlorine of defluorinate chlorine top of tower
Steam is condensed within the condenser, and condensate liquid then is delivered into fluorine chlorine reclaimer.
3. the method for waste acid concentration defluorinating chlorine according to claim 1, it is characterized in that：The multiple-effect evaporation concentration is triple effect
It is concentrated by evaporation.
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| CN201510982827.1A CN105502307B (en) | 2015-12-24 | 2015-12-24 | The method and special purpose device of waste acid concentration defluorinating chlorine |
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| CN201510982827.1A CN105502307B (en) | 2015-12-24 | 2015-12-24 | The method and special purpose device of waste acid concentration defluorinating chlorine |
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| CN105502307B true CN105502307B (en) | 2017-09-01 |
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| CN106823759A (en) * | 2017-02-28 | 2017-06-13 | 中国恩菲工程技术有限公司 | Defluorinate chlorine device |
| CN106882777B (en) * | 2017-04-06 | 2018-08-14 | 南通三圣石墨设备科技股份有限公司 | A kind of purifying phosphoric acid concentration technology |
| CN107670315A (en) * | 2017-09-30 | 2018-02-09 | 无锡英罗唯森科技有限公司 | Sulphuric acid concentration system and technique |
| CN109078351B (en) * | 2018-09-17 | 2023-09-05 | 杭州东日节能技术有限公司 | Defluorination chlorine tower and process and device for removing fluorine and chlorine in sulfuric acid by adopting same |
| CN112387096A (en) * | 2020-10-16 | 2021-02-23 | 楚雄滇中有色金属有限责任公司 | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium |
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| CN201109712Y (en) * | 2007-09-04 | 2008-09-03 | 冯圣君 | Apparatus for removing inorganic salt in diluted acid during enriching process |
| CN101428760B (en) * | 2008-12-22 | 2010-08-11 | 冯圣君 | Method and device for recycling hydrochloric acid and ferrous chloride with acid washing phosphorization waste liquor of steel wire rope |
| CN102424368B (en) * | 2011-09-27 | 2016-04-06 | 东营方圆有色金属有限公司 | Hot blast method of enrichment removes the technique of F, Cl, As in dirty acid |
| US9150440B2 (en) * | 2012-05-10 | 2015-10-06 | The National Titanium Dioxide Co. Ltd. (Cristal) | Method for purification of spent sulfuric acid from titanium dioxide rutile industry |
| CN104909507B (en) * | 2015-06-02 | 2017-05-24 | 河南双屿新材料科技有限公司 | Contaminated acid concentrating and recycling method |
| CN205328617U (en) * | 2015-12-24 | 2016-06-22 | 南通三圣石墨设备科技股份有限公司 | Device of dirty sour concentrated defluorinate chlorine |
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Denomination of invention: Method and dedicated device for concentrated defluorination and chlorine removal of polluted acid Granted publication date: 20170901 Pledgee: Bank of Communications Co.,Ltd. Nantong Branch Pledgor: NANTONG SUNSHINE GRAPHITE EQUIPMENT TECHNOLOGY Co.,Ltd. Registration number: Y2024980000877 |
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