CN110368894B - 一种去除废水中氟离子的高效除氟剂及其制备方法 - Google Patents
一种去除废水中氟离子的高效除氟剂及其制备方法 Download PDFInfo
- Publication number
- CN110368894B CN110368894B CN201910596276.3A CN201910596276A CN110368894B CN 110368894 B CN110368894 B CN 110368894B CN 201910596276 A CN201910596276 A CN 201910596276A CN 110368894 B CN110368894 B CN 110368894B
- Authority
- CN
- China
- Prior art keywords
- fly ash
- magnetic
- substance
- mixture
- wastewater
- 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
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 54
- 239000011737 fluorine Substances 0.000 title claims abstract description 54
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 54
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002351 wastewater Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 fluorine ions Chemical class 0.000 title claims abstract description 22
- 239000010881 fly ash Substances 0.000 claims abstract description 93
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 5
- 230000002431 foraging effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 3
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 238000006115 defluorination reaction Methods 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 6
- 238000005341 cation exchange Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract 2
- 238000000926 separation method Methods 0.000 abstract 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000011403 purification operation Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical class [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明提供一种去除废水中氟离子的高效除氟剂及其制备方法,所述的除氟剂由磁性粉煤灰、碳酸钠、盐酸、电石渣、氢氧化钠、稀土元素和氯化铁制备而成,利用稀土元素改性粉煤灰,提高粉煤灰的阳离子交换量和氟的去除率,然后利用电石渣和Fe2O3对改性粉煤灰进行磁化,使粉煤灰具有磁性,并进一步提高材料的吸附性能,便于除氟后进行分离,最后将磁性粉煤灰作原料,通过焙烧、酸浸和陈化制备成除氟剂。本发明制备的除氟剂对氟离子的吸附性能高,材料具有磁性便于后期沉淀分离,降低了废水净化操作成本,具有很好的经济效益。
Description
技术领域
本发明属于废水处理技术领域,特别涉及一种废水中氟离子去除的高效复合除氟剂及其制备方法。
背景技术
工业上,含氟矿石开采、金属冶炼、铝加工、焦炭、玻璃、电子、电镀、化肥、农药等行业排放的废水中常含有高浓度的氟化物,造成环境污染。除氟工艺研究一直是国内外环保及卫生领域的重要课题。目前国内外常用的废水除氟药剂大致分为两类:钙盐沉淀法除氟药剂和吸附法除氟药剂。吸附法除氟药剂主要有活性氧化铝、斜发沸石、活性氧化镁等,近年来,还报道了羟基磷灰石、氧化锆和氢氧化铈等氟吸附容量较高的吸附剂。
发明专利ZL201310723159.1一种天然矿物负载型纳米除氟剂的制备方法,其方法包括高温活化处理、酸活化处理、碱活化处理与金属盐反应。由于天然沸石具有较强的机械强度,其内部充满了细微的孔穴和通道,利用其作为纳米除氟材料的载体,在水流的条件下仍可以有效的将纳米材料固定在其内部的孔道内,从而避免纳米材料的团聚与流失,提高其吸附氟的能力,并且可再生重复利用,降低了除氟的成本。该发明的除氟剂具有较大的比表面积,能够提供较多的活性位点实现对氟高吸附容量,可广泛应用于高氟地表水、地下水净化处理及含氟污水处理等方面。但是该发明存在除氟剂消耗量大,不易于回收,同时沉淀量大不易于后期处理等缺陷。
发明专利ZL201310569409.0一种除氟药剂及其制备方法,所述除氟药剂中含有稀土元素,所述除氟药剂中还含有聚丙烯酰胺。该发明所述的药剂,其除氟原理是属于离子沉淀法去除氟离子,氟离子与稀土元素离子结合形成氟化稀土沉淀,氟化稀土不溶于水,通过离子共沉作用去除水中的氟离子,因此具有很好的选择性,生成的氟化稀土回收用于稀土冶炼。适用于废水中、低浓度氟离子污染因子的去除,其特点是除氟效果好且稳定,处理成本低,生成的氟化稀土可回收。但该发明的药剂对氟的吸附率不高,不适用于高浓度的含氟废水,同时沉淀处理难度大。
因此,开发高效除氟药剂,便于后期沉淀处理回收氟,对废水处理具有重大的意义。
发明内容
针对现有除氟药剂存在的吸附效率低、沉淀不易于收集处理、药剂不可再利用等缺陷,本发明提供一种去除废水中氟离子的高效除氟剂及其制备方法。
本发明是通过以下技术方案实现的:
一种去除废水中氟离子的高效除氟剂,由以下重量份数比组分制备而得:磁性粉煤灰15~40份,碳酸钠5~8份,氯化铁2~6份,盐酸A 15~20份;
所述的磁性粉煤灰和碳酸钠质量比为(3~5):1;
所述的盐酸A浓度为10~12mol/L,用量为磁性粉煤灰份数的0.5~1倍。
如上所述的去除废水中氟离子的高效除氟剂的制备方法,包括以下步骤:
(1)将磁性粉煤灰和碳酸钠混合,置于800~900℃的马弗炉中煅烧活化2~3h后,取出冷却至室温,得到活化物;
(2)在活化物中加入盐酸A,于105℃条件下酸浸1.5~2h,得到酸浸物;
(3)在酸浸物中加入氯化铁使pH调节至5.0,然后在温度25~30℃下熟化24h,即得到除氟剂;
本发明以磁性粉煤灰为主原料通过碱改和盐改结合制备成除氟剂,粉煤灰是煤粉燃烧后的产物,是一种疏松多孔物质,含有丰富的Si、Al、Fe、Ca、Mg、等物质,可通过阳离子交换对废水中的氟离子进行吸附,本发明通过对粉煤灰进行磁性化,便于后期沉淀的回收,然后利用碳酸钠助剂提高粉煤灰中铝铁的浸出率,从而提高阳离子交换率,再以通过氯化铁引入氯离子增加铁盐、铝盐的溶解度,进一步提高了粉煤灰对氟的吸附效果。
作为本发明的进一步改进,所述的磁性粉煤灰的制备方法如下:
(1)按照固液比为(1~3):(15~25):(2~4)称取四氧化三铁、去离子水和氨水,首先将四氧化三铁溶解于去离子水中,在80℃下水浴加热,然后逐滴加入氨水,持续搅拌反应1~1.5h,得到磁性溶液;
所述的氨水质量分数为25%;
(2)将改性粉煤灰研磨至60~80目,得到粉煤灰粉,按照粉煤灰粉与电石渣质量比1:(1~3)将两者混合,并充分研磨得到研磨物,然后按照固液比为1:(7~10)将研磨物加入到磁性溶液中混合均匀,得到混合物;
(3)将混合物在马弗炉内600℃下煅烧1~1.5h得到煅烧物,取出冷却至室温;
(4)于煅烧物中加入等质量的去离子水进行陈化24h,得到陈化物,然后将陈化物于80~110℃恒温箱内晶化4~8h得到晶化材料,最后用去离子水将晶化材料洗至中性,60℃下真空干燥,即得到磁性粉煤灰;
磁分离技术设备简单、能耗低,可以利用外加磁场的作用分离废水中的磁性物质,本发明通过在粉煤灰中加入磁性物质四氧化三铁,对粉煤灰进行磁化改性,利用强碱废渣电石渣作为磁化助剂,同时渗入粉煤灰中,提高本发明除氟剂的吸附量从而提高处理量,同时降低后期沉淀回收的难度;
电石渣是电石水解后的固体废弃物,其主要成分为氢氧化钙及少量硫化物、磷化物、氧化物、氧化镁、氧化铁、二氧化硅等,保水性强,强碱性,可以作为粉煤灰磁改性的助剂;电石渣表面结构疏松,粒间分布尺寸差异很大的孔隙,能与低价金属阳离子发生阳离子交换作用,因此可以与粉煤灰结合形成吸附性能更强的物质,能进一步提高除氟效率;电石渣溶于水中形成的氢氧化钙溶液易吸收空气中的CO2而形成CaCO3胶体,这种胶结作用能够显著提升本发明除氟剂的强度和水稳定性。
作为本发明的进一步改进,所述的改性粉煤灰制备方法如下:
(1)将粉煤灰与盐酸B按照固液比(2~4):1在磁力搅拌器上以200~300r/min,90~95℃搅拌酸洗1h至pH为7,于105℃烘干后,研磨过200目筛得到处理粉煤灰,
所述的盐酸B的浓度为2~4mol/L;
(2)将处理粉煤灰与氢氧化钠溶液按照固液比1:5混合均匀,接上冷凝装置在95~100℃水浴中反应8~12h,取出水洗至pH为7左右,105℃烘干得纯净粉煤灰;
所述的氢氧化钠浓度为2~4mol/L;
(3)按照固液比为1:(15~25),在纯净粉煤灰中加入质量浓度为0.1%~3%的稀土元素溶液,然后在气浴摇床中以150~200r/min、40~60℃恒温处理24h,取出水洗至中性,最后在105℃下烘干得到改性粉煤灰。
稀土元素对阴离子氟具有很强的吸附性,利用稀土元素对粉煤灰进行改性,提高了其阳离子交换容量的同时,还提高了氟的去除率,使本发明的除氟剂能对高浓度的废水具有很好的除氟效果,稀土元素含量过高会与粉煤灰形成配位络合物,堵塞粉煤灰和电石渣的孔道,因此稀土元素的使用量不能过高;
作为本发明的进一步改进,所述的稀土元素溶液为氯化镧、氯化铈、氯化镨、氯化钕中的一种。
本发明的有益效果:
1、本发明的除氟剂以粉煤灰为主材料,通过对粉煤灰进行稀土元素改性,并将电石渣渗入进行结合,提高了粉煤灰对氟的吸附能力,能有效除去高浓度废水中的氟,以电石渣作为助剂进行改性,提高了除氟剂的稳定性,并利用电石渣提高除氟剂对氟的吸附性能,以废治废,大大提高了原料利用率,具有很好的经济效益和社会效益。
2、本发明的除氟剂主材料粉煤灰经过磁化改性,便于后期对沉淀进行回收处理,降低了下游处理工艺的成本,提高了除氟效率,同时除氟剂可回收利用,减少废水处理成本。
具体实施方式
下面结合实施例对本发明进一步说明。
实施例1
一种去除废水中氟离子的高效除氟剂,由磁性粉煤灰15份,碳酸钠5份,氯化铁2份,10mol/L的盐酸A 15份制备而得;
所述的除氟剂的制备方法包括以下步骤:
(1)将磁性粉煤灰和碳酸钠混合,置于800℃的马弗炉中煅烧活化2h后,取出冷却至室温,得到活化物;
(2)在活化物中加入盐酸A,于105℃条件下酸浸1.5h,得到酸浸物;
(3)在酸浸物中加入氯化铁使pH调节至5.0,然后在温度25℃下熟化24h,即得到除氟剂;
所述的磁性粉煤灰的制备方法如下:
(1)按照固液比为1:15:2称取四氧化三铁、去离子水和氨水,首先将四氧化三铁溶解于去离子水中,在80℃下水浴加热,然后逐滴加入氨水,持续搅拌反应1h,得到磁性溶液;
所述的氨水质量分数为25%;
(2)将改性粉煤灰研磨至60目,得到粉煤灰粉,按照粉煤灰粉与电石渣质量比1:1将两者混合,并充分研磨得到研磨物,然后按照固液比为1:7将研磨物加入到磁性溶液中混合均匀,得到混合物;
(3)将混合物在马弗炉内600℃下煅烧1h得到煅烧物,取出冷却至室温;
(4)于煅烧物中加入等质量的去离子水进行陈化24h,得到陈化物,然后将陈化物于80℃恒温箱内晶化4h得到晶化材料,最后用去离子水将晶化材料洗至中性,60℃下真空干燥,即得到磁性粉煤灰;
所述的改性粉煤灰制备方法如下:
(1)将粉煤灰与2mol/的L盐酸B按照固液比2:1在磁力搅拌器上以200r/min,90℃搅拌酸洗1h至pH为7,于105℃烘干后,研磨过200目筛得到处理粉煤灰,
(2)将处理粉煤灰与2mol/L的氢氧化钠溶液按照固液比1:5混合均匀,接上冷凝装置在95℃水浴中反应8h,取出水洗至pH为7左右,105℃烘干得纯净粉煤灰;
(3)按照固液比为1:15,在纯净粉煤灰中加入质量浓度为0.1%的氯化镧溶液,然后在气浴摇床中以150r/min、40℃恒温处理24h,取出水洗至中性,最后在105℃下烘干得到改性粉煤灰;
本实施例的除氟剂的添加量为:100L废水中添加6L,废水pH为5,废水水温为25℃。
实施例2
一种去除废水中氟离子的高效除氟剂,由磁性粉煤灰40份,碳酸钠8份,氯化铁6份,12mol/L的盐酸A 20份制备而得;
所述的除氟剂的制备方法包括以下步骤:
(1)将磁性粉煤灰和碳酸钠混合,置于900℃的马弗炉中煅烧活化3h后,取出冷却至室温,得到活化物;
(2)在活化物中加入盐酸A,于105℃条件下酸浸2h,得到酸浸物;
(3)在酸浸物中加入氯化铁使pH调节至5.0,然后在温度30℃下熟化24h,即得到除氟剂;
所述的磁性粉煤灰的制备方法如下:
(1)按照固液比为3:25:4称取四氧化三铁、去离子水和氨水,首先将四氧化三铁溶解于去离子水中,在80℃下水浴加热,然后逐滴加入氨水,持续搅拌反应1.5h,得到磁性溶液;
所述的氨水质量分数为25%;
(2)将改性粉煤灰研磨至60~80目,得到粉煤灰粉,按照粉煤灰粉与电石渣质量比1:3将两者混合,并充分研磨得到研磨物,然后按照固液比为1:10将研磨物加入到磁性溶液中混合均匀,得到混合物;
(3)将混合物在马弗炉内600℃下煅烧1.5h得到煅烧物,取出冷却至室温;
(4)于煅烧物中加入等质量的去离子水进行陈化24h,得到陈化物,然后将陈化物于110℃恒温箱内晶化8h得到晶化材料,最后用去离子水将晶化材料洗至中性,60℃下真空干燥,即得到磁性粉煤灰;
所述的改性粉煤灰制备方法如下:
(1)将粉煤灰与4mol/L的盐酸B按照固液比4:1在磁力搅拌器上以300r/min,95℃搅拌酸洗1h至pH为7,于105℃烘干后,研磨过200目筛得到处理粉煤灰,
(2)将处理粉煤灰与4mol/L的氢氧化钠溶液按照固液比1:5混合均匀,接上冷凝装置在100℃水浴中反应12h,取出水洗至pH为7左右,105℃烘干得纯净粉煤灰;
(3)按照固液比为1:25,在纯净粉煤灰中加入质量浓度为3%的氯化铈溶液,然后在气浴摇床中以200r/min、60℃恒温处理24h,取出水洗至中性,最后在105℃下烘干得到改性粉煤灰;
本实施例的除氟剂的添加量为:100L废水中添加4L,废水pH为7,废水水温为30℃。
实施例3
一种去除废水中氟离子的高效除氟剂,由磁性粉煤灰20份,碳酸钠5份,氯化铁5份,11mol/L的盐酸A 20份制备而得;
所述的除氟剂的制备方法包括以下步骤:
(1)将磁性粉煤灰和碳酸钠混合,置于860℃的马弗炉中煅烧活化3h后,取出冷却至室温,得到活化物;
(2)在活化物中加入盐酸A,于105℃条件下酸浸2h,得到酸浸物;
(3)在酸浸物中加入氯化铁使pH调节至5.0,然后在温度28℃下熟化24h,即得到除氟剂;
所述的磁性粉煤灰的制备方法如下:
(1)按照固液比为1.5:20:2.5称取四氧化三铁、去离子水和氨水,首先将四氧化三铁溶解于去离子水中,在80℃下水浴加热,然后逐滴加入氨水,持续搅拌反应1h,得到磁性溶液;
所述的氨水质量分数为25%;
(2)将改性粉煤灰研磨至70目,得到粉煤灰粉,按照粉煤灰粉与电石渣质量比1:2将两者混合,并充分研磨得到研磨物,然后按照固液比为1:8将研磨物加入到磁性溶液中混合均匀,得到混合物;
(3)将混合物在马弗炉内600℃下煅烧1.5h得到煅烧物,取出冷却至室温;
(4)于煅烧物中加入等质量的去离子水进行陈化24h,得到陈化物,然后将陈化物于90℃恒温箱内晶化6h得到晶化材料,最后用去离子水将晶化材料洗至中性,60℃下真空干燥,即得到磁性粉煤灰;
所述的改性粉煤灰制备方法如下:
(1)将粉煤灰与3mol/L的盐酸B按照固液比3:1在磁力搅拌器上以300r/min,95℃搅拌酸洗1h至pH为7,于105℃烘干后,研磨过200目筛得到处理粉煤灰,
(2)将处理粉煤灰与3mol/L的氢氧化钠溶液按照固液比1:5混合均匀,接上冷凝装置在98℃水浴中反应10h,取出水洗至pH为7左右,105℃烘干得纯净粉煤灰;
(3)按照固液比为1:22,在纯净粉煤灰中加入质量浓度为1.5%的氯化钕素溶液,然后在气浴摇床中以180r/min、50℃恒温处理24h,取出水洗至中性,最后在105℃下烘干得到改性粉煤灰;
本实施例的除氟剂的添加量为:100L废水中添加5L,废水pH为10,废水水温为40℃。实施例1~3除氟剂处理含氟废水的效果见表1。
表1 实施例1~3除氟剂处理废水效果
对比例
以专利ZL201310569409.0实施例1~3制备的除氟药剂作为对比与本发明实施例制备的除氟药剂进行废水处理对比,具体结果见表2。
由上表可知,与专利ZL201310569409.0实施例1~3制备的除氟药剂对比,本发明实施例制备的除氟剂对含氟废水具有很好的处理效果。
以上实施例仅为本发明的示例性实施例,不用于限制本发明,本发明的保护范围由权利要求书限定。本领域人员可以在本发明的实质和保护范围内,对本发明做出各种修改或等同替换,这种修改或等同替换也应视为落在本发明的保护范围内。
Claims (2)
1. 一种去除废水中氟离子的高效除氟剂的制备方法,其特征在于,所述的除氟剂采用以下重量份数比组分制备而得:磁性粉煤灰15~40份,碳酸钠5~8份,氯化铁2~6份,盐酸A15~20份;
所述的磁性粉煤灰和碳酸钠质量比为(3~5):1;
所述的盐酸A浓度为10~12mol/L,用量为磁性粉煤灰份数的0.5~1倍;
所述去除废水中氟离子的高效除氟剂的制备方法,包括以下步骤:
(1)将磁性粉煤灰和碳酸钠混合,置于800~900℃的马弗炉中煅烧活化2~3h后,取出冷却至室温,得到活化物;
(2)在活化物中加入盐酸A,于105℃条件下酸浸1.5~2h,得到酸浸物;
(3)在酸浸物中加入氯化铁使pH调节至5.0,然后在温度25~30℃下熟化24h,即得到除氟剂;
所述的磁性粉煤灰的制备方法如下:
(1)按照固液比为(1~3):(15~25):(2~4)称取四氧化三铁、去离子水和氨水,首先将四氧化三铁溶解于去离子水中,在80℃下水浴加热,然后逐滴加入氨水,持续搅拌反应1~1.5h,得到磁性溶液;
所述的氨水质量分数为25%;
(2)将改性粉煤灰研磨至60~80目,得到粉煤灰粉,按照粉煤灰粉与电石渣质量比1:(1~3)将两者混合,并充分研磨得到研磨物,然后按照固液比为1:(7~10)将研磨物加入到磁性溶液中混合均匀,得到混合物;
(3)将混合物在马弗炉内600℃下煅烧1~1.5h得到煅烧物,取出冷却至室温;
(4)于冷却后的煅烧物中加入等质量的去离子水进行陈化24h,得到陈化物,然后将陈化物于80~110℃恒温箱内晶化4~8h得到晶化材料,最后用去离子水将晶化材料洗至中性,60℃下真空干燥,即得到磁性粉煤灰;
所述的改性粉煤灰制备方法如下:
(1)将粉煤灰与盐酸B按照固液比(2~4):1在磁力搅拌器上以200~300r/min,90~95℃搅拌酸洗1h至pH为7,于105℃烘干后,研磨过200目筛得到处理粉煤灰,
所述的盐酸B的浓度为2~4mol/L;
(2)将处理粉煤灰与氢氧化钠溶液按照固液比1:5混合均匀,接上冷凝装置在95~100℃水浴中反应8~12h,取出水洗至pH为7,105℃烘干得纯净粉煤灰;
所述的氢氧化钠溶液浓度为2~4mol/L;
(3)按照固液比为1:(15~25),在纯净粉煤灰中加入质量浓度为0.1%~3%的稀土元素溶液,然后在气浴摇床中以150~200r/min、40~60℃恒温处理24h,取出水洗至中性,最后在105℃下烘干得到改性粉煤灰。
2.根据权利要求1所述的去除废水中氟离子的高效除氟剂的制备方法,其特征在于,所述的稀土元素溶液为氯化镧、氯化铈、氯化镨、氯化钕溶液中的一种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910596276.3A CN110368894B (zh) | 2019-07-03 | 2019-07-03 | 一种去除废水中氟离子的高效除氟剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910596276.3A CN110368894B (zh) | 2019-07-03 | 2019-07-03 | 一种去除废水中氟离子的高效除氟剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110368894A CN110368894A (zh) | 2019-10-25 |
CN110368894B true CN110368894B (zh) | 2022-09-13 |
Family
ID=68251752
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910596276.3A Active CN110368894B (zh) | 2019-07-03 | 2019-07-03 | 一种去除废水中氟离子的高效除氟剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110368894B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111116164B (zh) * | 2020-02-19 | 2021-11-19 | 国能朗新明环保科技有限公司 | 一种粉煤灰基多孔除氟材料及其制备方法和应用 |
CN113735235A (zh) * | 2021-09-24 | 2021-12-03 | 华北电力大学(保定) | 一种处理含铅废水的粉煤灰基磁混凝剂及制备方法、应用和再生方法 |
CN114733479B (zh) * | 2022-03-15 | 2024-04-26 | 合肥学院 | La2O3改性航天炉粗渣滤饼多孔吸附材料的制备方法及应用 |
CN116764610B (zh) * | 2023-07-24 | 2024-03-08 | 中节能(山东)循环经济有限公司 | 一种水体除氟剂及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103739048A (zh) * | 2013-11-13 | 2014-04-23 | 南京格洛特环境工程股份有限公司 | 一种除氟药剂及制备方法 |
CN104069833A (zh) * | 2014-07-27 | 2014-10-01 | 青岛博睿林新材料有限公司 | 一种改性玉米须吸附氟的吸附剂 |
CN104858204A (zh) * | 2015-04-08 | 2015-08-26 | 安徽理工大学 | 一种粉煤灰磁珠的资源化利用方法 |
CN105854815A (zh) * | 2016-06-16 | 2016-08-17 | 马鞍山市顺达环保设备有限公司 | 一种吸附容量大的烟气吸附剂 |
CN107570109A (zh) * | 2017-10-20 | 2018-01-12 | 新疆大学 | 一种电石渣处理粉煤灰实现其资源化利用的方法 |
CN107952414A (zh) * | 2017-10-30 | 2018-04-24 | 安徽铭能保温科技有限公司 | 一种含油废水吸附剂及其制备方法 |
CN108421526A (zh) * | 2018-03-16 | 2018-08-21 | 锡林郭勒职业学院 | 一种水热/酸浸两步制备粉煤灰除氟剂的方法及应用 |
-
2019
- 2019-07-03 CN CN201910596276.3A patent/CN110368894B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103739048A (zh) * | 2013-11-13 | 2014-04-23 | 南京格洛特环境工程股份有限公司 | 一种除氟药剂及制备方法 |
CN104069833A (zh) * | 2014-07-27 | 2014-10-01 | 青岛博睿林新材料有限公司 | 一种改性玉米须吸附氟的吸附剂 |
CN104858204A (zh) * | 2015-04-08 | 2015-08-26 | 安徽理工大学 | 一种粉煤灰磁珠的资源化利用方法 |
CN105854815A (zh) * | 2016-06-16 | 2016-08-17 | 马鞍山市顺达环保设备有限公司 | 一种吸附容量大的烟气吸附剂 |
CN107570109A (zh) * | 2017-10-20 | 2018-01-12 | 新疆大学 | 一种电石渣处理粉煤灰实现其资源化利用的方法 |
CN107952414A (zh) * | 2017-10-30 | 2018-04-24 | 安徽铭能保温科技有限公司 | 一种含油废水吸附剂及其制备方法 |
CN108421526A (zh) * | 2018-03-16 | 2018-08-21 | 锡林郭勒职业学院 | 一种水热/酸浸两步制备粉煤灰除氟剂的方法及应用 |
Also Published As
Publication number | Publication date |
---|---|
CN110368894A (zh) | 2019-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110368894B (zh) | 一种去除废水中氟离子的高效除氟剂及其制备方法 | |
JP3954009B2 (ja) | 炭酸ガスの固定化方法 | |
US11332380B2 (en) | Method for aluminum-enhanced dealkalization of red mud and separation and recovery of aluminum and iron | |
CN106517621B (zh) | 含氯化铵废水的回收利用工艺 | |
CN106830244B (zh) | 一种从含氟酸性废水中分离回收氟和酸的方法 | |
CN107954623B (zh) | 一种固体废弃物表面原位生长纳米颗粒的制备方法 | |
CN112169748B (zh) | 一种吸附剂及其制备方法和应用 | |
CN104760980B (zh) | 一种高纯超细氧化铝粉的制备工艺 | |
CN111905690A (zh) | 一种利用粉煤灰制备水体脱氮除磷增氧复合材料的方法 | |
CN112316924A (zh) | 一种煤矸石基多孔复合材料及其制备方法和应用 | |
CN107641714A (zh) | 一种含铅原料湿法回收处理方法 | |
CN111498864B (zh) | 一种磁性沸石材料及其制备方法、应用 | |
CN110563190A (zh) | 一种电解锰渣渗滤液的处理方法 | |
CN114702055A (zh) | 利用可循环氨基酸浸提剂从高钙粉煤灰中制备高纯碳酸钙的方法 | |
CN113083219A (zh) | 一种黄磷炉渣制备脱氮除磷吸附剂的方法及应用 | |
CN104724740B (zh) | 一种高纯超细氢氧化铝粉的制备方法 | |
CN104934089A (zh) | 一种放射性废水处理方法 | |
CN110407250B (zh) | 一种含砷废渣转化为砷铝石稳定化处理并回收硫磺的方法 | |
CN105771997A (zh) | 一种脱碱赤泥的制备方法及其用途 | |
CN101306850B (zh) | 复合高效硅藻土净水剂及制备方法 | |
CN110479207A (zh) | 一种电解锰渣微波碱熔活化制备高吸附量沸石的方法 | |
CN109851084A (zh) | 降低含锰废水中氨氮、钙、镁离子含量的资源化处理方法 | |
CN115041127B (zh) | 一种磁性铈基金属氧化物吸附剂及其制备方法和应用 | |
CN106395925A (zh) | 一种聚合硫酸铁净水剂的制备方法 | |
CN107381705B (zh) | 一种相变调控分离回收水中多种阳离子重金属的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20240109 Address after: 230000, No. 201-03, Block A, South Zone, Phase III, Huguang Road, Hefei Area, China (Anhui) Free Trade Pilot Zone, Hefei City, Anhui Province Patentee after: Anhui Santuo Environmental Technology Co.,Ltd. Address before: 546500 office building of Management Committee of Heshan industrial transformation Park, Laibin City, Guangxi Zhuang Autonomous Region Patentee before: Heshan Chunxu Environmental Protection Technology Co.,Ltd. |
|
TR01 | Transfer of patent right |