CN102001689B - Method for recycling side product of sodium hydrogen sulfate generated by production of chlorine dioxide - Google Patents
Method for recycling side product of sodium hydrogen sulfate generated by production of chlorine dioxide Download PDFInfo
- Publication number
- CN102001689B CN102001689B CN2010105249402A CN201010524940A CN102001689B CN 102001689 B CN102001689 B CN 102001689B CN 2010105249402 A CN2010105249402 A CN 2010105249402A CN 201010524940 A CN201010524940 A CN 201010524940A CN 102001689 B CN102001689 B CN 102001689B
- Authority
- CN
- China
- Prior art keywords
- sodium
- sulfate
- sodium sulfate
- water
- hot water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 title claims abstract description 62
- 229910000342 sodium bisulfate Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title abstract description 48
- 235000019398 chlorine dioxide Nutrition 0.000 title abstract description 25
- 239000004155 Chlorine dioxide Substances 0.000 title abstract description 23
- 239000006227 byproduct Substances 0.000 title abstract description 8
- 238000004064 recycling Methods 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 65
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 61
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000012065 filter cake Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims description 35
- 150000002978 peroxides Chemical class 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000012856 packing Methods 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 18
- 238000001914 filtration Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000011734 sodium Substances 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000003570 air Substances 0.000 description 14
- 239000007790 solid phase Substances 0.000 description 12
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 11
- 239000002253 acid Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004076 pulp bleaching Methods 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000406668 Loxodonta cyclotis Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical class [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen salt Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Abstract
The invention relates to a method for recycling a side product of sodium hydrogen sulfate generated by production of chlorine dioxide, which comprises the steps of: mixing sodium hydrogen sulfate obtained through filtration with water according to the weight ratio of 0.6-1.57:1 and injecting in a double decomposition reactor for stirring reaction, wherein the reaction conditions are as follows: the temperature is 70-100 DEG C, the stirring speed is 10-30r/min and the stirring time is 10-25min; then filtering a sodium hydrogen sulfate suspension reaching interchange balance of materials, and washing filter cakes through combined spraying of hot water and hot water containing diluted alkali liquor to obtain wet medium sodium sulfate solids with PH value of 6-9; and then scattering, drying and packaging the materials to obtain a medium sodium sulfate solid finished product. The method has the advantages of simple process, high conversion efficiency, dried and clean products and high recycling efficiency, and is economic and practical; and the obtained medium sodium sulfate solid can be used for producing products of sodium sulfate, glass, porcelain glaze and the like.
Description
Technical field
The present invention relates to the chlorine dioxide production field, specifically is a kind of method that reclaims the sub product sodium acid sulfate of producing the dioxide peroxide generation.
Technical background
Dioxide peroxide is a kind of strong oxidizer, and stabilized chlorine dioxide is thought the effective sterilant and the disinfection sanitizer of excellent property by the World Health Organization, also is good papermaking SYNTHETIC OPTICAL WHITNER.From 1830s, the beginning suitability for industrialized production, 1000 chlorine dioxide production factories at present have an appointment in NA and Europe.Current China has realized the production domesticization of small-sized sterilization with chlorine dioxide production equipment; But; For on-site prepn and the on-the-spot large-scale chlorine dioxide preparation system that uses digestion; The domestic development that also is in, the large-scale chlorine dioxide production system that existing papermaking enterprise adopts is suite of equipment in import of technique.
The main application of dioxide peroxide is association with pulp bleaching and drinking water disinfection, dioxide peroxide be used for association with pulp bleaching have high whiteness, whiteness stable, keep intensity and the low hypotoxic characteristics of color of draining, its unique superior property is that any other chemical is incomparable so far.In view of the high toxicity of ClO 2 bleaching meliority and chlorine bleaching, it is one of chemical of association with pulp bleaching that dioxide peroxide has been recommended by National Development and Reform Committee, and progressively eliminates the chlorine bleaching process.
The preparation method of dioxide peroxide mainly is divided into two big types: electrolytic process and chemical method.Electrolytic process is VAL-DROP direct and hydrochloric acid reaction generation dioxide peroxide in device that the salt solution electrolysis is obtained.External successively the exploitation with sodium-chlor, VAL-DROP and Textone is the novel method of ionogen electrolytic synthesis dioxide peroxide since the seventies, and this method equipment has high input, complex process, and current also not obtaining promoted.
Chemical method is divided into again: VAL-DROP reduction method and Textone reduction method.The VAL-DROP reduction method comprises that R1 is to 12 kinds of methods such as R12.Wherein, the R8 method has been called the most widely used now chlorine dioxide generation since industriallization in 1985.The improved methyl alcohol method of the inferior company of U.S.'s A Bulaite/Weir is called the R8 method, is a kind of method that adopts VAL-DROP, sulfuric acid and methanol production dioxide peroxide.Under strong acid, certain temperature, vacuum condition in titanium vessels reduction VAL-DROP continuous production chlorine dioxide with high purity, ClO2 gas with the absorption of freezing water, obtains having finite concentration ClO2 solution through cooling off after.Reaction system acidity constantly generates sodium acid sulfate usually at 8.0N-8.2N in the bearing reaction reaction system, be also referred to as sesquialter sodium sulfate, after operation is with salt loading, separates out with the crystallized form of sodium acid sulfate.This method reaction formula is following:
6NaClO
3+4H
2SO
4+CH
3OH＝6ClO
2+2Na
2SO
4·NaHSO
4+CO
2+5H
2O (1)
30NaClO
3+20H2SO4+7CH
3OH＝30ClO
2+10Na
2SO
4·NaHSO
4+6HCOOH+CO
2+23H
2O (2)
12NaClO
3+8H
2SO
4+6CH
3OH＝6ClO
2+3Cl
2+4Na
2SO
4·NaHSO
4+6CO
2+18H
2O (3)
Wherein reaction (1) and reaction (2) are main reaction, and reaction (3) is side reaction.
For the sustainability that keeps reacting, adopt filtering form that crystal is shifted out from system, obtain containing the solid sodium acid sulfate of certain water.This by product can be used for pulp mill, together gets into the burning of alkali stove to make the additional compound of this factory's sulphur loss, promptly to mix with the concentrated black liquid of this factory, and sodium sulfate obtains reclaiming the slip house that is used for this factory with the form of sodium sulphite.Yet because the slurrying production environment is airtight relatively, the loss of sulphur obviously reduces, and the sodium sulfate that needs to replenish also significantly reduces, and causes this material to become useless by product.
Because sodium acid sulfate is strongly-acid, corrodibility is strong, and using value is low, is difficult to obtain effective Application Areas.If will excavate its application potential, be necessary to be translated into neutral sodium sulfate.The method that realizes the most easily is exactly an acid-base neutralisation, has been irreversible trend but adopt dioxide peroxide to substitute chlorine at present, has needed the neutral sodium acid sulfate more and more since like this, and the result makes sodium hydroxide and chlorine imbalance in the chlor-alkali plant.Sodium hydroxide concentration increases, and the consumption of chlorine reduces, and the result is that production cost increases.In addition, because the acid of sodium acid sulfate is neutralized, must production cost further be increased to chlorine dioxide generator continuous supplementation sulfuric acid to keep required acidity.
Use the suggestion that the initial stage had proposed to solve sodium acid sulfate as far back as the R8 method; In will warm washing water from the reverse feeding washing column of crystallization by product of chlorine dioxide generator; The crystallisate of carrying reaction medium secretly is separated, also can make sodium acid sulfate change into sodium bisulfate or neutral sodium sulfate.This method water consumption is very big, when being back to use chlorine dioxide generator to the acidic liq that obtains, need evaporate a large amount of water for keeping continuous production, has increased consumption of heat energy to a great extent.On the other hand because a large amount of steam mixes with dioxide peroxide, give absorb the lower or water consumption of used freezing water temp more the great talent be enough to make aqueous solution of chlorine dioxide to keep stable, the ClO 2 solution concentration that therefore obtains is lower, application is very inconvenient.
Patent publication No. is to describe the solid phase byproduct sodium acid sulfate that makes from chlorine dioxide production in the technical scheme of US4325934 to contact with methanol aqueous solution with generation solid phase sodium sulfate.The weight ratio of this technology institute's water and sodium acid sulfate is 0.6: 1-0.8: 1, and the weight ratio of methyl alcohol and sodium acid sulfate is 0.3: 1-0.8: 1.After washing excessive methyl alcohol, this technology gas from acidic solution is back to use chlorine dioxide generator.This just need wash operation for gas and send out the expense expense.
Patent publication No. is to describe in the technical scheme of CA1118184 solid phase byproduct is contacted with warm water, presses multistage dialysis-washing operation, and sodium acid sulfate is effectively changed into neutral sodium sulfate.But find often to stop up, 1 ton of dioxide peroxide of every production, producer evaporation load increases 3-4 ton water approximately.
Patent publication No. is to describe sodium acid sulfate in the technical scheme of CN1067224A to contact for some time with water-bearing media; Under 40 ℃ of-70 ℃ of temperature, make acid effectively change at least the sodium sulfate that part is the solid crystal form, and generate that to have total acid equivalent concentration be 4.8 the aqueous solution.The water medium of describing is water, sodium chlorate solution, methanol solution, sodium chloride solution, and this technology is to produce 1 ton of dioxide peroxide to increase by 2 tons of water of evaporation approximately, overcomes the some shortcomings of aforesaid method to a certain extent.But also there is following deficiency in this method: the solubleness of sodium sulfate is higher in (1) described TR; Be unfavorable for that very sodium sulfate crystal separates out; Exist precipitation efficiency low; Invent water and sodium acid sulfate 0.6: 1-0.8 according to this: 1 The Best Mixed ratio is 60%-70% 40 ℃ of following theoretical conversion efficient, adds with also dissolving part in the warm water washing process, and its productive rate is merely 31.25%-37.15% as a result.If reach the effectively amount of shifting out, need repeatedly circulation, increase the load of the operation of system, even cause filtering system to be moved continuously, in case break down, cause serious loss to subsequent production.(2) want to improve the crystal amount of separating out, the most effectively way is exactly to improve the ratio of sodium acid sulfate and water, certainly will cause acidity increase in the system, causes separating out hydrogen salt increase in the crystal, causes transformation efficiency to descend.(3) though add VAL-DROP, sodium-chlor and methyl alcohol can utilize homo-ion and solvent effect improves transformation efficiency, increase rate is very limited also to cause adverse influence to production.Use such as a large amount of sodium-chlor,, cause chlorine content increase in the chlorine dioxide by reuse and chlorine dioxide generator; VAL-DROP remains in the product, and corrodibility is strong, is unfavorable for follow-up use, moreover VAL-DROP is comparatively expensive, and a large amount of VAL-DROP addings certainly will be carried secretly by the sulfuric acid crystal and caused damage, and increase running cost; The adding of methyl alcohol, volatile quantity is big under the higher temperature of description, behind the entering scrubbing tower, dissolves in washing water and is discharged contaminate environment or increases subsequent treatment cost.(4) sodium sulfate that obtains contains large quantity of moisture and a spot of sulfuric acid and sodium pyrosulfate, and pH value is less than 1, and corrodibility is big, can't adopt common drying plant dry, returns follow-up packing, transportation and use and brings great inconvenience or increase extra-pay.
Because a variety of causes, these methods enough do not have the industrial production magnetism.At present a lot of manufacturing enterprises all adopt direct discharging to the processing of sodium bisulfate, and useful sodium sulfate and acid are not used, and return environment and cause great pollution.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that reclaims the by product acid sodium sulfate that produces when producing dioxide peroxide, makes the sub product sodium acid sulfate be converted into drying, purified neutral sodium sulfate.
The present invention solves the problems of the technologies described above with following technical scheme: the present invention reclaims the method for the sub product sodium acid sulfate of producing the dioxide peroxide generation and is undertaken by following process step: will contain sodium acid sulfate crystalline reaction mother liquor earlier and filter; Then sodium acid sulfate filter cake that obtains and water are 0.6-1.57 by weight ratio: 1 mixes stirring reaction in the injection double decomposition reactor; Reaction conditions is: temperature is that 70-100 ℃, stirring velocity are that 10-30r/min, churning time are 10-25min; Make solid-liquid two phase exchange of substance reach balance; To reach exchange of substance equilibrated sodium bisulfate suspension filtered then; Filter cake sprays washing with hot water and the hot water combination that contains sig water, makes the neutral sodium sulfate solid pH value that obtains be controlled at 6-9; And then the neutral sodium sulfate solid that will wet breaks up, and utilizes temperature to carry out drying for 120-140 ℃ warm air again, and packing obtains neutral sodium sulfate solid finished product at last.
The preferable reaction temperature of said double decomposition reactor is 85-95 ℃.
Said sodium acid sulfate filter cake and water blended weight proportion preferable range are 0.8-1.31: 1.
The said proportion that reaches exchange of substance equilibrated sodium bisulfate suspension-s is 1.37-1.76.
The hot water that said sprinkling washing leaching cake is used is 70-80 ℃ with the hot water temperature of containing sig water, and the hot water that contains sig water can be to adopt the hot water that contains sodium hydroxide or yellow soda ash or sodium hydrogencarbonate.
Said sodium acid sulfate filter cake sprays the wine washing with 70-80 ℃ of hot water earlier before injecting double decomposition reactor, perhaps utilize washing to filter the saturated sodium sulfate hot soln of low acidity that filter cake obtains the second time and wash, and control this solution acidity and be not higher than 6 equivalents.
Said wet neutral sodium sulfate solid is to send into that fluidized-bed is broken up, drying, and the hot air temperature of employing preferably remains on 130 ℃.
The inventive method technology is simple, and transformation efficiency is high, and recycling efficient is high, economically feasible, and the neutral sodium sulfate finished product drying that obtains is pure, can be used for making products such as sodium sulphite, glass and enamel.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
Below in conjunction with accompanying drawing the inventive method is further described:
Earlier will be from being the mother liquor of the chlorine dioxide generator of raw material production dioxide peroxide with methyl alcohol, sulfuric acid, VAL-DROP; Filter through the 1# filter; And 70-80 ℃ of hot water of sprinkling; Utilize the saturated sodium sulphate hot soln of low acidity (acidity is not higher than 6 equivalents) of washing 2# filter cake to replace hot water to wash afterwards; The acidic liq that obtains returns chlorine dioxide generator; Sodium acid sulfate filter cake that obtains and water are by weight for 0.6-1.57: 1 ratio is injected in the double decomposition reactor and carried out stirring reaction, and the condition of reaction is: temperature is that 70-100 ℃, stirring velocity are that 10-30r/min, churning time are 10-25min, makes solid-liquid two phase exchange of substance reach balance; The sodium bisulfate suspension-s that will reach exchange of substance equilibrated proportion then and be 1.37-1.76 filters through the 2# filter; Filter cake is 70-80 ℃ hot water and carries out the washing of disacidify degree with the hot water combination that contains sig water with temperature, make to obtain moisture about 10% wet neutral sodium sulfate solid pH value and be controlled at 6-9, and the saturated sodium sulphate hot soln of the low acidity that obtains is sent to 1# filter washing sodium acid sulfate filter cake; And then the neutral sodium sulfate solid that will wet falls in the wet feed surge bunker through elephant trunk, sends into fluidized-bed by quantitative self-conveyor feed again, and material is broken up through the device of breaing up that is located at front end earlier; Loose material gets into the heating area under control backward and places on the air distribution plate, and the ambient air that is blasted by gas blower becomes through the vapor heat exchanger heat exchange that 120-140 ℃ hot blast is laggard goes into the equal air compartment of fluidized-bed and be upward through air distribution plate and contact with material, and material is carried low suspension secretly in air-flow hot blast; Just as the boiling water that boils; Under the effect of bubble, violent seething beated, and under the zigzag motion state, evenly fully contacts with air-flow, heat exchange; Produce violent bump with the inner-heating tube surface simultaneously; Carry out ferocious heat transfer, mass transfer, accomplish drying process, dried most of material is in the fluidized-bed discharge hole for discharge; Packing obtains neutral sodium sulfate solid finished product; Air blasts vapor heat exchanger by gas blower and carries out that heat exchange is laggard goes into fluidized-bed; Contact completion fluidisation, heat exchange with material after; Carrying water vapor, partial material and waste heat (used heat) secretly; Be drawn into through system's induced draft fan and enter atmosphere after cloth bag separator separates, purifies, the isolating sodium sulfate of cloth bag separator is sent to the packing machine packing through worm conveyor.
The present invention has confirmed that to the efficient conversion of neutral sodium sulfate the mixing of solid phase sodium acid sulfate and water reaches the equilibrated reaction conditions for realizing sodium acid sulfate, comprises temperature of reaction, reaction times and stirring velocity etc.Said temperature of reaction is 70-100 ℃, preferably remains on 85-95 ℃, and the said reaction times is 10-25min, and said mixing speed is controlled at 10-30r/min, keeps certain stirring velocity to be beneficial to the dissolving of sodium acid sulfate.
The present invention uses earlier hot wash for realizing sodium acid sulfate before the efficient conversion of neutral sodium sulfate is being injected multiple anti-decomposition reactor to the 1# filter cake; The saturated hot soln of lower acidity sulfuric acid sodium of utilizing washing 2# filter cake to obtain afterwards substitutes hot water and washs; The acidity of the saturated hot soln of lower acidity sulfuric acid sodium is not higher than 6 equivalents; Can prevent effectively that the dissolving of filter cake from returning producer, improve effectively and transform.
The present invention realizes effective conversion and convenient storage, transportation and the use of sodium acid sulfate to neutral sodium sulfate; The 2# filter cake is carried out the washing of disacidify degree; Adopt hot water or hot water and the hot water combination washing that contains sig water, the neutral that obtains pH value and the be 6-9 solid sodium sulfate that wets.
The present invention is for realizing the effective conversion of sodium acid sulfate to neutral sodium sulfate, and the drying, the purified neutral sodium sulfate that obtain convenient storage, transportation and use adopt fluidized-bed that wet neutral sodium sulfate is carried out drying, and the packing of dry back obtains neutral sodium sulfate finished product.
The inventive method can realize sodium acid sulfate following to the efficient theoretical analysis that transforms of neutral sodium sulfate:
Sodium acid sulfate (Na
3H (SO
4)
2) ionization takes place in the aqueous solution:
Na
3H(SO
4)
2→3Na
++SO
4 2-+H
+ (4)
Na
3H (SO
4)
2Mix Na in the solution of formation with water
2SO
4When surpassing its saturation concentration, concentration will separate out Na
2SO
4, this moment, system existed with liquid phase two mutually conformal formulas with solid phase, between solid phase and liquid phase, exchange of substance took place.This under certain conditions exchange will reach balance, that is:
Solid phase is to liquid-phase conversion: NaHSO
4→ Na
++ SO
4 2-+ H
+(5)
Na
2SO
4→2Na
++SO
4 2- (6)
Liquid phase transforms to solid phase: 2Na
++ SO
4 2-→ Na
2SO
4(7)
Na
++SO
4 2-+H
+→NaHSO
4 (8)
The solid phase sodium acid sulfate mixes at first react (4) with water, show as the solid phase sodium acid sulfate and in water, disperse and dissolve.Be dissolved into to a certain degree that sodium sulfate concentration surpasses its saturation concentration in the ie in solution; To react (7) and react (8); Almost react simultaneously (5) and react (6), the total amount of reaction (5) only at this moment and reaction (6) transfer of material is less than reaction (7) and react (8).Finish reaction until reaction (4) and reach balance, the total amount of reaction (5) at this moment and reaction (6) transfer of material equals the weight of reaction (7) and reaction (8) transfer of material, i.e. dissolved NaHSO from solid phase
4And Na
2SO
4Amount and the NaHSO that from liquid phase, separates out
4And Na
2SO
4The crystalline amount equates.
Because vitriolic solubleness is bigger, so H+ concentration is lower than NaHSO under the finite concentration
4The amount of separating out less.Apparently be presented as Na in the solid phase
3H (SO
4)
2Constantly dissolve and Na
2SO
4Constantly separate out body, shown in reaction (9), thereby realize the conversion of sodium acid sulfate to sodium sulfate.
2Na
3H (SO
4)
2+ water → Na
2SO
4+ 2Na
++ 2SO
4 2-+ 2H
++ water (9)
The sodium sulfate crystal that obtains obtains wet sodium sulfate solid through the filter filtration, and residual a small amount of sulfuric acid and sodium pyrosulfate neutralize under the cleaning function of diluted alkaline hot soln, shown in reaction (10) and (11).
NaHSO
4+NaOH＝Na
2SO
4+H
2O (10)
H
2SO
4+2NaOH＝Na
2SO
4+2H
2O (11)
Wet sodium sulfate solid contact, takes place heat exchange and deviates from moisture with warm air in fluidized drier, as reacting shown in (12).
Wet sodium sulfate+warm air → exsiccant sulfuric acid+malaria (12)
Embodiment 1
In chlorine dioxide generator, ClO
2Generate simultaneously; The sub product sodium acid sulfate is also constantly at the producer intercrystalline; Open 1# sodium sulfate transferpump the liquid in the part producer (containing the bisulphate sodium crystal in the liquid) is delivered to the filtration of 1# filter; And spray 70-80 ℃ of hot wash sodium acid sulfate filter cake, and the acidic liq that obtains returns chlorine dioxide generator, and sodium acid sulfate that obtains and water are that 1: 1 ratio is injected in the replacement(metathesis)reaction container continuously by weight ratio.Under heating state, keeping temperature of reactor is 85 ℃, after stopping 20min under the rotating speed of 30r/min, obtains exchange of substance equilibrated proportion and be 1.73 sodium bisulfate suspension-s; Open 2# sodium sulfate transferpump double decomposition reactor bottom suspension-s is delivered to the filtration of 2# filter; And spray 80 ℃ of hot water and 80 ℃ of hot alkali water washing leaching cakes, detect the filter cake pH value, and adjusting hot alkali water consumption is controlled in the scope of 6-9 the pH value of neutral sodium sulfate filter cake; The saturated metabisulfite solution of low acidity (this solution acidity is not higher than 6 equivalents) that filtration obtains is sent to the 1# filter and substitutes hot wash sodium bisulfate filter cake; Moisture about 10% the neutral sodium sulfate that obtains is fallen in the wet feed surge bunker through elephant trunk, sends into fluidized-bed by quantitative self-conveyor feed again, breaks up through the device of breaing up that is located at front end earlier; Loose material gets into the heating area under control backward and places on the air distribution plate; The ambient air that is blasted by gas blower changes 130 ℃ hot blast into through vapor heat exchanger and gets into the equal air compartment of fluidized-bed and be upward through air distribution plate and contact with material, and material is carried low suspension secretly in air-flow hot blast, just as the boiling water that boils; Under the effect of bubble; Violent seething beated, and under the zigzag motion state, evenly fully contacts, heat exchange the violent bump of the surperficial generation of while and inner-heating tube with air-flow; Carry out ferocious heat transfer, mass transfer, accomplish drying process.Dried most of material is in the fluidized-bed discharge hole for discharge, and packing obtains neutral sodium sulfate solid finished product.The air of carrying water vapor, partial material and waste heat (used heat) secretly is drawn into through system's induced draft fan and enters atmosphere after cloth bag separator separates, purifies, and the isolating sodium sulfate of cloth bag separator is sent to the packing machine packing through worm conveyor.Along with ClO in chlorine dioxide generator
2Constantly generate, its sub product sodium acid sulfate also continuously obtains reclaiming with the situation of the purified neutral sodium sulfate of drying.
Below be in the present embodiment the raw material sodium acid sulfate with transform after the composition synopsis of the neutral sodium sulfate of finished product (the acid-base neutralisation method is measured hydrogen radical ion amount and is converted into NaHSO
4Content, down together)
| Sample | NaHSO 4Content, % | Na 2SO 4Content, % | PH value |
| Raw material (sodium bisulfate) | 39.5 | 60.5 | ＜1 |
| Sample after the conversion (neutral sodium sulfate) | 0 | 100 | 8 |
Embodiment 2:
With 800gNa
3H (SO
4)
2Insert and fill in the 1000g clear water, be stirred and heated to 70 ℃, continue down to stir 25 minutes at 70 ℃ with the 25r/min rotating speed; Obtain two phase exchange of substance equilibrated proportions and be 1.71 crystal suspension-s, under vacuum action, leach mother liquor, filter cake is with 70 ℃ of hot washes 1-2 time; And the use temperature is 70 ℃ 0.2% sodium hydroxide hot soln washing; Obtain moisture 12.67% pH value and be 8.8 sodium sulfate solid, utilize 140 ℃ hot air dries again, obtain neutral sodium sulfate solid finished product.
Raw material in the present embodiment is following with the composition synopsis that transforms the back sample:
| Sample | NaHSO 4Content, % | Na 2SO 4Content, % | PH value |
| Raw material (sodium acid sulfate) | 39.5 | 60.5 | ＜1 |
| Transform back sample (neutral sodium sulfate) | 0 | 100 | 8.8 |
Embodiment 3:
With 1310gNa
3H (SO
4)
2Insert and fill in the 1000g clear water, be stirred and heated to 100 ℃, continue down to stir 15 minutes at 100 ℃ with the 10r/min rotating speed; Obtain two phase exchange of substance equilibrated proportions and be 1.72 crystal suspension-s, under vacuum action, leach mother liquor, filter cake is with 80 ℃ of hot washes 1-2 time; And the use temperature is 70 ℃ 0.1% yellow soda ash hot soln washing; Obtain moisture 9.08% pH value and be 6.5 sodium sulfate solid, utilize 130 ℃ hot air dries again, obtain neutral sodium sulfate solid finished product.
Raw material in the present embodiment is following with the composition synopsis that transforms the back sample:
| Sample | NaHSO 4Content, % | Na 2SO 4Content, % | PH value |
| Raw material (sodium acid sulfate) | 39.5 | 60.5 | ＜1 |
| Transform back sample (neutral sodium sulfate) | 0 | 100 | 6.5 |
Claims (3)
1. one kind is reclaimed the method for producing the sub product sodium acid sulfate that dioxide peroxide produces; The process step that it is characterized in that it is: will contain sodium acid sulfate crystalline reaction mother liquor earlier and filter; Then sodium acid sulfate filter cake that obtains and water are 0.8-1.31 by weight ratio: 1 mixes stirring reaction in the injection double decomposition reactor; Reaction conditions is: temperature is that 85-95 ℃, stirring velocity are that 10-30r/min, churning time are 10-25min; Make solid-liquid two phase exchange of substance reach balance, the proportion that contains sodium sulfate crystal suspension-s during balance is 1.37-1.76, will reach exchange of substance equilibrated sodium bisulfate suspension filtered then; Filter cake sprays washing with 70-80 ℃ hot water with the hot water combination that contains sig water, makes the wet neutral sodium sulfate solid pH value that obtains be controlled at 6-9; And then the neutral sodium sulfate solid that will wet sends into fluidized-bed and breaks up, and utilizes temperature to carry out drying for 120-140 ℃ warm air, and packing obtains neutral sodium sulfate solid finished product at last.
2. the method that the sub product sodium acid sulfate of dioxide peroxide generation is produced in said recovery according to claim 1, it is characterized in that: the hot water that contains sig water that said sprinkling washing leaching cake is used is meant the hot water that contains sodium hydroxide or yellow soda ash or sodium hydrogencarbonate.
3. the method that the sub product sodium acid sulfate of dioxide peroxide generation is produced in said recovery according to claim 1; It is characterized in that: said sodium acid sulfate filter cake is before injecting double decomposition reactor; Earlier spray washing with 70-80 ℃ of hot water; Perhaps utilize washing to filter the saturated sodium sulfate hot soln of low acidity that filter cake obtains for the second time and wash, and control this solution acidity and be not higher than 6 equivalents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105249402A CN102001689B (en) | 2010-10-29 | 2010-10-29 | Method for recycling side product of sodium hydrogen sulfate generated by production of chlorine dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105249402A CN102001689B (en) | 2010-10-29 | 2010-10-29 | Method for recycling side product of sodium hydrogen sulfate generated by production of chlorine dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102001689A CN102001689A (en) | 2011-04-06 |
| CN102001689B true CN102001689B (en) | 2012-05-02 |
Family
ID=43809439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105249402A Active CN102001689B (en) | 2010-10-29 | 2010-10-29 | Method for recycling side product of sodium hydrogen sulfate generated by production of chlorine dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102001689B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523754B (en) * | 2013-10-17 | 2015-05-27 | 南京工大环境科技有限公司 | Comprehensive utilization technology of chlorine dioxide reaction raffinate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5116595A (en) * | 1991-04-22 | 1992-05-26 | Tenneco Canada Inc. | Metathesis of acidic by-product of chlorine dioxide generating process |
| CA2148462C (en) * | 1992-11-09 | 1999-08-31 | Herbert C. Scribner | Metathesis of acidic by-product of chlorine dioxide generating process |
| US5399332A (en) * | 1993-10-20 | 1995-03-21 | Sterling Canada, Inc. | Dynamic leaching procedure for metathesis |
| CA2188721C (en) * | 1995-11-02 | 2005-04-26 | Sterling Canada, Inc. | Process for metathesis |
| US6126702A (en) * | 1998-03-09 | 2000-10-03 | International Paper Company | Apparatus and method for treating sesquisulfate waste streams |
-
2010
- 2010-10-29 CN CN2010105249402A patent/CN102001689B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102001689A (en) | 2011-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101648725B (en) | Method for preparing industrial calcium chloride | |
| CN101336207A (en) | Production of sodium sesquicarbonate and sodium carbonate monohydrate | |
| CA1083776A (en) | Preparation of sodium carbonate anhydride | |
| CN101092240A (en) | New technique for preparing sodium hydroxide | |
| CN105439095A (en) | Method and device for preparing sodium chlorite through comprehensive method chlorine dioxide process | |
| CN101519189A (en) | Method and device for preparing basic magnesium hypochlorite by using waste chlorine | |
| CN101519383B (en) | Process for jointly producing cyanuramide, sodium carbonate and ammonium chloride by using carbamide | |
| CN102502507A (en) | Preparation device and technology for chlorine dioxide | |
| CN102806004A (en) | Magnesium desulfurization byproduct recovery process | |
| CN102001689B (en) | Method for recycling side product of sodium hydrogen sulfate generated by production of chlorine dioxide | |
| CN101544384B (en) | Method for reclaiming the accessory product acidic mirabilite when producing chlorine dioxide | |
| CN102515112A (en) | Method for preparing sodium sulfide from hydrogen sulfide waste gas produced in production of viscose fibre | |
| CN101200285A (en) | Method for producing polychloroethylene and hydrochloric acid | |
| CN102862964B (en) | Device and method for producing monopotassium phosphate by using double decomposition | |
| CN103318958B (en) | Separation and refining method of arsenic trioxide | |
| CN103980214B (en) | The processing method of waste gas waste water in a kind of sym-closene production process | |
| CN105947985B (en) | A kind of chlorine dioxide preparation method of recyclable sodium acid sulfate | |
| CN112340700B (en) | System and method for recycling chlorine from waste mother liquor of bleaching powder | |
| CN104163410A (en) | Method for preparing calcium phosphite from industrial sodium hypophosphite waste residues | |
| CN103991851A (en) | New process for green and cyclic production of hydrazine hydrate | |
| CN1341557A (en) | Joint production process of salt and salt-cake | |
| CN101671087B (en) | Method for recovering reagent grade sodium nitrate from waste liquid of bismuth subnitrate production | |
| CN1179413A (en) | Method for producing formic acid and coproducing various sodium phosphate salts by acidifying sodium formate with perphosphoric acid | |
| CN102849777A (en) | Production process of active copper oxide | |
| CN102295376A (en) | Recycling treatment method for lignin production wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for recycling side product of sodium hydrogen sulfate generated by production of chlorine dioxide Effective date of registration: 20171013 Granted publication date: 20120502 Pledgee: Bank of Communications Ltd. the Guangxi Zhuang Autonomous Region branch Pledgor: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: 2017450000009 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20191119 Granted publication date: 20120502 Pledgee: Bank of Communications Ltd. the Guangxi Zhuang Autonomous Region branch Pledgor: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: 2017450000009 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for recycling side product of sodium hydrogen sulfate generated by production of chlorine dioxide Effective date of registration: 20191121 Granted publication date: 20120502 Pledgee: Nanning Urban Rural Credit Cooperative Association Pledgor: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2019450000023 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20201119 Granted publication date: 20120502 Pledgee: Nanning Urban Rural Credit Cooperative Association Pledgor: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2019450000023 |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: Intersection of Dongcheng Avenue and Dongcheng Road in Heli Park, Ningguo Economic and Technological Development Zone, Ningguo City, Xuancheng City, Anhui Province Patentee after: Anhui Boshike Environmental Protection Technology Co.,Ltd. Country or region after: China Address before: 530007 No.8 Gaoxin 5th Road, Nanning City, Guangxi Zhuang Autonomous Region Patentee before: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240507 Address after: Intersection of Dongcheng Avenue and Dongcheng Road in Heli Park, Ningguo Economic and Technological Development Zone, Ningguo City, Xuancheng City, Anhui Province Patentee after: Anhui Boshike Environmental Protection Technology Co.,Ltd. Country or region after: China Patentee after: Guangxi Boshike Environmental Technology Co.,Ltd. Address before: Intersection of Dongcheng Avenue and Dongcheng Road in Heli Park, Ningguo Economic and Technological Development Zone, Ningguo City, Xuancheng City, Anhui Province Patentee before: Anhui Boshike Environmental Protection Technology Co.,Ltd. Country or region before: China |