CN105435733A - High-phosphate-adsorption-activity large-particle-size zirconium hydroxide, and preparation and use methods and application thereof - Google Patents
High-phosphate-adsorption-activity large-particle-size zirconium hydroxide, and preparation and use methods and application thereof Download PDFInfo
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- CN105435733A CN105435733A CN201510989982.6A CN201510989982A CN105435733A CN 105435733 A CN105435733 A CN 105435733A CN 201510989982 A CN201510989982 A CN 201510989982A CN 105435733 A CN105435733 A CN 105435733A
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- zirconium hydroxide
- zirconium
- phosphate radical
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- 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
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- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- 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
- C02F2101/105—Phosphorus compounds
Abstract
The invention discloses a high-phosphate-adsorption-activity large-particle-size zirconium hydroxide. The specific area is 300-700 m<2>/g; the pore volume is 0.15-0.3 cm<3>/g; the pore size is 1.5-3.0nm; and the particle size D10 is greater than or equal to 5 mu m and smaller than or equal to 15 mu m, the particle size D50 is greater than or equal to 20 mu m and smaller than or equal to 30 mu m, and the particle size D90 is greater than or equal to 40 mu m and smaller than or equal to 90 mu m. The invention also discloses preparation and use methods and application of the zirconium hydroxide. The prepared zirconium hydroxide has favorable selective adsorption effects on H2PO4<->, HPO4<2-> and PO4<3-> in the water body, and is free from the influence of other impurity ions; and the adsorption capacity can reach 0.7 mmol/g or above. The zirconium hydroxide has the advantages of favorable biocompatibility, no toxicity and no harm, can lower the dialysis pressure and energy consumption when being mixed with large-particle-size SiO2, and can be used as a medical dialysis material to regulate the phosphorus content in blood.
Description
Technical field
The invention belongs to technical field of water body purification, be specifically related to Large stone zirconium hydroxide of a kind of high phosphate radical adsorption activity and preparation method thereof.
Background technology
Phosphate anion (PO
4 3-) be a kind of common anion in Chemical Manufacture, its existence can bring significant damage to production and environment, and algae in water especially can be made in water body to breed rapidly, thus causes red tide etc.In daily life, if phosphate anion too high levels in blood of human body, the liver of human body, heart are worked the mischief.
At present, industrially chemical precipitation method, bioanalysis, electric flocculence and absorption method etc. are mainly contained for removing the method for phosphorus in water body.Wherein chemical precipitation Application comparison is extensive, and the mode adding lime precipitation after usually adding the flocculant of phosphate anion again reaches the effect of dephosphorization, but the more difficult removal of hypophosphorous acid root; Bioanalysis dephosphorization efficiency is lower, usual and chemical precipitation method acting in conjunction purifying water body, but is the increase in cost; Can reach purifying water body object by the high voltage low current tertiary treatment technology of electric flocculence, but energy consumption is large.Absorption method dephosphorization not only efficiency is high, and sorbing material can recycle through desorption, in the paper studies of " research of modification bentonite in treatment phosphorus-containing wastewater ", such as Zhang Junbao etc. show that modified bentonite has 96.78% clearance for trace phosphorus solion, but adsorption capacity only has 0.096mmol/g.Contrast with other dephosphorization materials, zirconium hydroxide is used as the advantages such as adsorbent is applied in water body purification field and has that efficiency is high, equipment investment is low, simple to operate and easy recovery for the trace phosphorus solion adsorption treatment zirconium hydroxide that then adsorption capacity and clearance can reach 0.7mmol/g and 95% especially Large stone, high-specific surface area; Zirconium hydroxide also has nontoxic, harmless characteristic simultaneously, can be used for preparing haemodialysis material, regulates the content of phosphorus in blood, has boundless development prospect.
Summary of the invention
The object of this invention is to provide a kind of Large stone zirconium hydroxide of reusable high phosphate radical adsorption activity with low cost.The present invention also provides preparation method and the using method of this Large stone zirconium hydroxide.
For realizing above object, technical scheme of the present invention is as follows:
A Large stone zirconium hydroxide for high phosphate radical adsorption activity, is characterized in that, specific area 300 ~ 700m
2/ g; Pore volume 0.15 ~ 0.3cm
3/ g; Aperture 1.5 ~ 3.0nm; Particle diameter 5 μm≤D
10≤ 15 μm, 20 μm≤D
50≤ 30 μm, 40 μm≤D
90≤ 90 μm; The amount of substance of every gram of zirconium hydroxide adsorb phosphate is not less than 0.7mmol.
Another technical problem that the present invention will solve is to provide a kind of preparation method of Large stone zirconium hydroxide of high phosphate radical adsorption activity, and step comprises:
A Large stone zirconium hydroxide for high phosphate radical adsorption activity, its preparation process is as follows:
(1) aqueous slkali that hydroxyl concentration is more than or equal to 0.5mol/L, is prepared;
(2), under 15 ~ 95 DEG C with the condition stirred add zirconium salt solution, slurry or solid, the pH controlling reaction end is 7 ~ 14, and then at 60 ~ 120 DEG C of ageing 2 ~ 36h, then at 60 ~ 100 DEG C, suction filtration obtains filter residue;
(3), add water the filter residue of acquisition making beating, wherein filter residue and water are by 1:1 ~ 4(weight ratio) mix, then under the condition stirred, slow dropping concentration is the weak acid of 0.5 ~ 9mol/L, controls acid adjustment terminal pH 2 ~ 7, and make pH stablize 20 ~ 120min 2 ~ 7, then suction filtration obtains solid sample;
In order to obtain better technique effect, aqueous slkali described in step (1) is one or more combinations in sodium hydroxide solution, potassium hydroxide solution, barium hydroxide solution or ammonia spirit; Zirconates described in step (2) is one or more combinations in zirconium carbonate, zirconium oxychloride, zirconium basic sulphate, acetic acid zirconium, zirconium iso-octoate; The water washing of the use of filter residue described in step (2) 50 ~ 100 DEG C 3 ~ 7 times; Weak acid described in step (3) is one or more combinations in acetic acid, propionic acid, lactic acid, citric acid, benzoic acid, hypochlorous acid; The water washing of the middle solid sample 50 ~ 100 DEG C of step (3) 3 ~ 7 times; After step (3), baking oven solid sample being put into 50 ~ 120 DEG C is dried, and the zirconium amount in Quality control is (with ZrO
2form is measured) at 55 ~ 80wt%.
The present invention also provides the using method of this Large stone zirconium hydroxide, and its step comprises:
(1), by the zirconium hydroxide powder of preparation and silica (SiO
2, particle diameter is 100 μm) and microballon mixes according to 1:1 ~ 4 mass ratio, then loads the filter of a column;
(2), compound concentration is 2.60mmol/L sodium dihydrogen phosphate, injects, the water body after the other end then can be purified, H with the speed that 10 ~ 20ml/min is constant from one end of pillar
2pO
4 1-, HPO
4 2-, PO
4 3-the clearance of ion reach more than 95%; With PO
4 3-metering, its adsorption capacity is not less than 0.7mmol/g, i.e. every gram of zirconium hydroxide PO that can adsorb
4 3-the amount of ionic species is not less than 0.7mmol.
In order to obtain better technique effect, step activates zirconium hydroxide after (2), zirconium hydroxide after step (2) being used is at 60 ~ 100 DEG C, with 1L containing 0.025 ~ 0.125mol/L aqueous slkali soaking 10 ~ 30min hydroxy suction filtration again, spend the filter residue that deionized water obtains for 3 ~ 7 times, then by filter residue and water mixing furnishing suspension, then its pH value 2 ~ 7 is regulated to make the high adsorption activity of product recovery to phosphate radical with weak acid.The method can process zirconium hydroxide after use 10 ~ 20 times repeatedly, and remains on more than 90% to the adsorption activity of phosphate radical.
The present invention also provides this Large stone zirconium hydroxide in haemodialysis to the adsorption applications of phosphate radical.
The principle of the inventive method is: this method provides a kind of zirconium hydroxide of Large stone of high phosphate radical adsorption activity, and its specific area is not less than 300m
2/ g, by hydroxyl and the H of zirconium hydroxide microparticle surfaces
2pO
4 -/ HPO
4 2-/ PO
4 3-ion exchange reaches the effect of adsorption cleaning water body.
The invention has the advantages that: the zirconium hydroxide prepared by (1) to H in water body
2pO
4 -, HPO
4 2-, PO
4 3-selective absorption is effective, and not by the impact of other foreign ions, adsorption capacity can reach more than 0.7mmol/g; (2) biocompatibility that the zirconium hydroxide tool prepared by is good is nontoxic, without harmfulness, with the SiO of Large stone
2used in combinationly effectively can reduce dialysate pressure, reduce energy consumption, can be used as the content that medical dialysis material regulates phosphorus in blood.(3) whole preparation process and equipment requirement are simple, and can high efficiente callback zirconium hydroxide by desorption, and again utilize, and produce without solid waste.
Accompanying drawing explanation
Fig. 1 is zirconium hydroxide dialysis testing process schematic diagram.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.
Embodiment 1
Preparation 20wt%Ba (OH)
2solution and 240g/LZrOCl
2solution, at Ba (OH) under 90 DEG C with the condition stirred
2zrOCl is added in solution
2solution, and control reaction end pH=8.0, at 60 DEG C of ageing 36h, then at 60 DEG C of suction filtrations, and obtain filter residue 3 times with the water diafiltration of 90 DEG C.By filter residue with water by 1:4(weight ratio) mix and pull an oar, then under the effect of stirring, slowly drip the spirit of vinegar of 0.83mol/L, control acid adjustment terminal pH=5.30, and stablize 20min under pH=5.30, then suction filtration also obtains solid sample 6 times with the water diafiltration of 90 DEG C.Sample being put into 50 DEG C of baking ovens oven dry makes zirconium amount be 60.65wt%, finally prepares Large stone zirconium hydroxide phosphate radical to high adsorption activity.
Embodiment 2
Preparation contains mixed alkali liquor and the 60wt%ZrOSO of 20wt%NaOH and 28wt%KOH respectively
4suspension, then 60 DEG C and stir conditions under by ZrOSO
4slurry is poured in NaOH and KOH solution, and controls reaction end pH=9.00, at 120 DEG C of ageing 2h, then at 100 DEG C of suction filtrations, and obtains filter residue 5 times with the water diafiltration of 50 DEG C.By filter residue with water by 1:1(weight ratio) mix and pull an oar, then the mix acid liquor that slow dropping acetic acid and citric acid form under the effect of stirring, in mix acid liquor, acetic acid and citric acid concentration are respectively 0.7mol/L and 0.75mol/L, control acid adjustment terminal pH=2.51, and stablize 60min at pH=2.51, then suction filtration also obtains sample 3 times with the water diafiltration of 50 DEG C.Sample being put into 120 DEG C of baking ovens oven dry makes zirconium amount be 70.83wt%, finally prepares Large stone zirconium hydroxide phosphate radical to high adsorption activity.
Embodiment 3
Preparation 50wt%KOH solution, adds ZrOCO under 90 DEG C with the condition stirred
3nH
2o solid, and control reaction end pH=12.08, at 80 DEG C of ageing 24h, then at 80 DEG C of suction filtrations, and obtain filter residue 4 times with the water diafiltration of 80 DEG C.By filter residue with water by 1:3(weight ratio) add water to mix and pull an oar, then under the effect of stirring, slowly drip rare propionic acid of 1.22mol/L, control acid adjustment terminal pH=6.04, and stablize 120min at pH=6.04, then suction filtration also obtains sample 4 times with the water diafiltration of 80 DEG C.Sample being put into 80 DEG C of baking ovens oven dry makes zirconium amount be 72.81wt%, finally prepares Large stone zirconium hydroxide phosphate radical to high adsorption activity.
Embodiment 4
Preparation 25wt% concentrated ammonia liquor and 240g/LZrOCl
2solution, adds ZrOCl under 30 DEG C with the condition stirred in ammonia spirit
2solution, and control reaction end pH=11.00, at 60 DEG C of ageing 16h, then at 60 DEG C of suction filtrations, and obtain filter residue 7 times with 60 DEG C of deionized water diafiltrations.By filter residue with water by 1:2(weight ratio) add water to mix and pull an oar, under the effect of stirring, then slowly drip rare lactic acid of 1.22mol/L, control acid adjustment terminal pH=3.50, and stablize 30min, then suction filtration is also with the water diafiltration 3 times of 60 DEG C.Sample being put into 60 DEG C of baking ovens oven dry makes zirconium amount be 58.47wt%, finally prepares Large stone zirconium hydroxide phosphate radical to high adsorption activity.
Each physical index of the sample prepared by table 1 embodiment 1 ~ 4
。
Embodiment 5
As shown in Figure 1, a kind of using method of Large stone zirconium hydroxide, its step comprises:
(1) by the zirconium hydroxide powder obtained by embodiment 2 and silica (SiO
2, particle diameter is 100 μm) and microballon mixes according to 1:1 mass ratio, then loads in the filter B of a column;
(2) compound concentration is that 2.60mmol/L sodium dihydrogen phosphate is placed in container A, and injected from one end of the filter B of column with the speed that 10 ~ 20ml/min is constant by constant flow pump, the other end then can collect the water body after being purified by container C, H
2pO
4 1-, HPO
4 2-, PO
4 3-the clearance of ion reach more than 95%; With PO
4 3-metering, its adsorption capacity is 0.83mmol/g, i.e. every gram of zirconium hydroxide PO that can adsorb
4 3-the amount of ionic species is 0.83mmol;
(3) until above-mentioned zirconium hydroxide no longer adsorb phosphate time, the said goods is soaked 10 ~ 30min suction filtration again by the NaOH solution of 1 liter of 0.075mol/L at 80 DEG C, spends deionized water and obtain filter residue 3 ~ 7 times; Then by filter residue and water mixing furnishing suspension, acetic acid (0.7mol/L) and citric acid (0.75mol/L) mix acid liquor is used to regulate the pH to 2.5 of zirconium hydroxide suspension again, and suction filtration obtains filter residue after pH=2.5 stablizes 10min, filter residue is used again the water diafiltration 4 times of 80 DEG C, then the dry recovery then completing zirconium hydroxide;
(4) zirconium hydroxide reclaimed is repeated by step (1)-(3), repeat 20 times and reclaim and adsorption test.Table 2 is that this zirconium hydroxide is to Phosphateadsorption amount and the relation table recycling number of times.
Table 2 zirconium hydroxide is recycled and performance change
。
Embodiment 6
Large stone zirconium hydroxide is to an adsorption applications for phosphate radical in haemodialysis, and its step comprises:
(1) the one-tenth assignment system sodium dihydrogen phosphate of simulate blood Main Inorganic Salts, test zirconium hydroxide is applied to the absorption property to phosphate radical in haemodialysis.By sodium dihydrogen phosphate 0.456g, the water-soluble solution of sodium chloride 6.82g, sodium acid carbonate 1.98g, sodium acetate 0.182g mixes, then drip several 37wt% concentrated hydrochloric acid and in 1L volumetric flask constant volume, control solution final pH=7.1;
(2) solution prepared is tested zirconium hydroxide obtained by embodiment 3, its method of testing flow process is with embodiment 5, flow chart as shown in Figure 1, for solution containing phosphate described in step (1) passes through test pole B through constant flow pump with 15ml/min speed in container A, in B, zirconium hydroxide mixes by 1:2 mass ratio with quartzy microballon, the every 10min of container C collects the liquid after primary purification, until there is phosphonium ion seepage, then phosphate ion concentration in test container C, finally calculating its adsorption capacity is 0.88mmol/g.
Claims (10)
1. a Large stone zirconium hydroxide for high phosphate radical adsorption activity, is characterized in that, specific area 300 ~ 700m
2/ g; Pore volume 0.15 ~ 0.3cm
3/ g; Aperture 1.5 ~ 3.0nm; Particle diameter 5 μm≤D
10≤ 15 μm, 20 μm≤D
50≤ 30 μm, 40 μm≤D
90≤ 90 μm; The amount of substance of every gram of zirconium hydroxide adsorb phosphate is not less than 0.7mmol.
2. the preparation method of the Large stone zirconium hydroxide of high phosphate radical adsorption activity according to claim 1, step comprises:
(1) aqueous slkali that hydroxyl concentration is more than or equal to 0.5mol/L, is prepared;
(2), under 15 ~ 95 DEG C with the condition stirred add zirconium salt solution, slurry or solid, the pH controlling reaction end is 7 ~ 14, and then at 60 ~ 120 DEG C of ageing 2 ~ 36h, then at 60 ~ 100 DEG C, suction filtration obtains filter residue;
(3), add water the filter residue of acquisition making beating, wherein filter residue and water are by 1:1 ~ 4(weight ratio) mix, then under the condition stirred, slow dropping concentration is the weak acid of 0.5 ~ 9mol/L, controls acid adjustment terminal pH 2 ~ 7, and make pH stablize 20 ~ 120min 2 ~ 7, then suction filtration obtains solid sample.
3. the preparation method of the Large stone zirconium hydroxide of high phosphate radical adsorption activity as claimed in claim 2, it is characterized in that, aqueous slkali described in step (1) is one or more combinations in sodium hydroxide solution, potassium hydroxide solution, barium hydroxide solution or ammonia spirit.
4. the preparation method of the Large stone zirconium hydroxide of high phosphate radical adsorption activity as claimed in claim 2, it is characterized in that, zirconates described in step (2) is one or more combinations in zirconium carbonate, zirconium oxychloride, zirconium basic sulphate, acetic acid zirconium, zirconium iso-octoate.
5. the preparation method of the Large stone zirconium hydroxide of high phosphate radical adsorption activity as claimed in claim 2, is characterized in that, the water washing of the use of filter residue described in step (2) 50 ~ 100 DEG C 3 ~ 7 times.
6. the preparation method of the Large stone zirconium hydroxide of high phosphate radical adsorption activity as claimed in claim 2, is characterized in that, weak acid described in step (3) is one or more combinations in acetic acid, propionic acid, lactic acid, citric acid, benzoic acid, hypochlorous acid.
7. the preparation method of the Large stone zirconium hydroxide of high phosphate radical adsorption activity as claimed in claim 2, is characterized in that, after step (3), baking oven solid sample being put into 50 ~ 120 DEG C is dried, and the zirconium amount in Quality control is (with ZrO
2form is measured) at 55 ~ 80wt%.
8. the using method of the Large stone zirconium hydroxide of high phosphate radical adsorption activity according to claim 1, its step comprises:
(1), by the zirconium hydroxide powder of preparation and silica (SiO
2, particle diameter is 100 μm) and microballon mixes according to 1:1 ~ 4 mass ratio, then loads the filter of a column;
(2), compound concentration is 2.60mmol/L sodium dihydrogen phosphate, injects, the water body after the other end then can be purified, H with the speed that 10 ~ 20ml/min is constant from one end of pillar
2pO
4 1-, HPO
4 2-, PO
4 3-the clearance of ion reach more than 95%; With PO
4 3-metering, its absorption appearance is not less than 0.7mmol/g.
9. the using method of the Large stone zirconium hydroxide of high phosphate radical adsorption activity as claimed in claim 8, it is characterized in that, step activates zirconium hydroxide after (2), zirconium hydroxide after step (2) being used is at 60 ~ 100 DEG C, with 1L containing 0.025 ~ 0.125mol/L aqueous slkali soaking 10 ~ 30min hydroxy suction filtration again, spend the filter residue that deionized water obtains for 3 ~ 7 times, then by filter residue and water mixing furnishing suspension, then its pH value 2 ~ 7 is regulated to make the high adsorption activity of product recovery to phosphate radical with weak acid.
10. the Large stone zirconium hydroxide of high phosphate radical adsorption activity according to claim 1 in haemodialysis to the adsorption applications of phosphate radical.
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|---|---|---|---|
| CN201510989982.6A CN105435733A (en) | 2015-04-21 | 2015-12-25 | High-phosphate-adsorption-activity large-particle-size zirconium hydroxide, and preparation and use methods and application thereof |
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|---|---|---|---|
| CN201510190313 | 2015-04-21 | ||
| CN2015101903132 | 2015-04-21 | ||
| CN201510989982.6A CN105435733A (en) | 2015-04-21 | 2015-12-25 | High-phosphate-adsorption-activity large-particle-size zirconium hydroxide, and preparation and use methods and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967263A (en) * | 2016-06-24 | 2016-09-28 | 何颖 | Water purifying device |
| CN106492743A (en) * | 2016-11-25 | 2017-03-15 | 陕西科技大学 | Doped meso-porous material Zr SBA 15 of zirconium and preparation method and application |
| CN113083214A (en) * | 2021-03-30 | 2021-07-09 | 山东大学 | Preparation method of mesoporous zirconium/lanthanum double hydroxide fiber and application of mesoporous zirconium/lanthanum double hydroxide fiber in purification of phosphate wastewater |
| CN114873773A (en) * | 2022-03-28 | 2022-08-09 | 青岛天尧新材料有限公司 | Method for treating phosphorus-containing wastewater |
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| US20040007531A1 (en) * | 2002-07-15 | 2004-01-15 | Bortun Anatoly I. | Hydrous zirconium oxide, hydrous hafnium oxide and method of making same |
| US20080121584A1 (en) * | 2005-10-14 | 2008-05-29 | Inframat Corporation | Methods of making water treatment compositions |
| CN101708862A (en) * | 2009-12-10 | 2010-05-19 | 江西晶安高科技股份有限公司 | Zirconium hydroxide solid-phase grinding synthesis method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040007531A1 (en) * | 2002-07-15 | 2004-01-15 | Bortun Anatoly I. | Hydrous zirconium oxide, hydrous hafnium oxide and method of making same |
| US20080121584A1 (en) * | 2005-10-14 | 2008-05-29 | Inframat Corporation | Methods of making water treatment compositions |
| CN101708862A (en) * | 2009-12-10 | 2010-05-19 | 江西晶安高科技股份有限公司 | Zirconium hydroxide solid-phase grinding synthesis method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967263A (en) * | 2016-06-24 | 2016-09-28 | 何颖 | Water purifying device |
| CN106492743A (en) * | 2016-11-25 | 2017-03-15 | 陕西科技大学 | Doped meso-porous material Zr SBA 15 of zirconium and preparation method and application |
| CN106492743B (en) * | 2016-11-25 | 2018-09-14 | 陕西科技大学 | Doped meso-porous material Zr-SBA-15 of zirconium and the preparation method and application thereof |
| CN113083214A (en) * | 2021-03-30 | 2021-07-09 | 山东大学 | Preparation method of mesoporous zirconium/lanthanum double hydroxide fiber and application of mesoporous zirconium/lanthanum double hydroxide fiber in purification of phosphate wastewater |
| CN114873773A (en) * | 2022-03-28 | 2022-08-09 | 青岛天尧新材料有限公司 | Method for treating phosphorus-containing wastewater |
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Inventor after: Qiu Caihua Inventor after: Chen Xiaowei Inventor after: Chen Meiling Inventor after: Wu Jiang Inventor after: Chen Shuanghua Inventor before: Li Chun Inventor before: Qiu Caihua Inventor before: Chen Xiaowei Inventor before: Chen Shuanghua Inventor before: Chen Meiling |
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Application publication date: 20160330 |
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| RJ01 | Rejection of invention patent application after publication |