CN106669606A - Adsorption and slow release filler for artificial wet land and preparation method thereof - Google Patents
Adsorption and slow release filler for artificial wet land and preparation method thereof Download PDFInfo
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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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
- B01J20/0203—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
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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Abstract
The invention belongs to the field of novel environmentally-friendly materials, and particularly relates to an adsorption and slow release filler for an artificial wet land and a preparation method of the adsorption and slow release filler. The preparation method of the filler comprises the following steps in sequence: acidic liquid immersion activation of a base body material, laminating the activated base body material with polyaniline, immersion compound treatment on the laminated base body material through a copper solution, and calcining and hole forming treatment of a biomass material and an adhesive which are mixed. The adsorption and slow release filler provided by the invention is large in adsorption amount and high in adsorption capacity; when pollutants, such as nitrogen and phosphorus, entering water cannot be completely absorbed by plants on the surface layer of the artificial wet land due to a large content, the filler can effectively adsorb the redundant pollutants; the filler also has slow release capacity; when the content of the pollutants such as the nitrogen and the phosphorus cannot meet the growth of the plants, the filler can slowly release nutritional substances such as the nitrogen and the phosphorus to meet the growth requirement of the plants. Main raw materials for preparing the adsorption and slow release filler are low-price products such as montmorillonoid, kaolin, attapulgite and a biomass material, so that the filler is low in production cost.
Description
Technical field
The invention belongs to environmental friendly material field, and in particular to a kind of adsorption sustained-release filler and its system for artificial swamp
Preparation Method.
Background technology
In recent years, China's water environment situation deteriorates increasingly, occur in that lake eutrophication, immediate offshore area red tide, river and
The problems such as organic contamination of reservoir, threaten the diversion safety of resident and the health of the people.Wastewater treatment work
Effects of purification quality is good, capital construction operating cost is low, energy consumption is low, maintenance management is simple, capacity of resisting impact load because it has for skill
The features such as strong, and can be that wild animal provide habitat, the aesthetic values of raising ecoscape, thus sanitary sewage,
The aspects such as industrial wastewater, agricultural area source sewage, urban storm runoff and eutrophication water are widely used
Current artificial swamp is all to intercept settle in sewage and can using the flourishing root of water plant and filler particles
The solid of flocculation, while being degraded to the harmful substance in sewage by the microorganism for being attached to plant root, reaches water quality
The purpose of purification.Existing Artificial Wetland Techniques are disadvantageous in that, when water quality and quantity has large change or water plant
During the season of withered harvesting, the water outlet through artificial swamp may cannot just meet requirement up to standard.
The content of the invention
To overcome deficiency of the prior art, the present invention provide it is a kind of can be used for the adsorption sustained-release filler of artificial swamp and its
Preparation method, one layer of adsorption sustained-release filler, when water body flows through, the pollution in water are laid in the packing layer of existing artificial swamp
A thing part is absorbed and used by plants, and a part is adsorbed by the adsorption sustained-release material, when the material concentration such as nitrogen phosphorus is smaller in water inlet
When cannot meet demand of plant growth, organic matter that filler slow release has been adsorbed in it and nitrogen phosphorus for plant growth needs,
When the material concentration such as nitrogen phosphorus is larger in water inlet, when plant cannot be adsorbed completely, it is possible to use the absorption property of sorbing material is to dirt
Unnecessary pollutant is adsorbed in water, so that water outlet meets requirement up to standard.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of adsorption sustained-release filler for artificial swamp
Preparation method, it comprises the following steps：
S1. activate：Soaked in matrix material input reactor after being screened with 200~2000 mesh sieves and with acid solution
Not yet, stir-activating 1-12h, centrifugation is simultaneously washed to neutrality, dries, and obtains final product activated matrix material, standby；
S2. overlay film：Activated matrix material in S1 is mixed with water, slurries are beaten to obtain, acid solution is added, sequentially added
Aniline and initiator, initiator are one or more in the persulfates such as sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate, and it can
Trigger aniline that polymerisation occurs simultaneously to be sufficiently mixed with matrix material, stirring at normal temperature reaction 2-8h, suction filtration, washing, drying, grind
Mill, sieving, obtain 200~2000 mesh overlay film matrix materials；
S3. it is combined：By the overlay film matrix material in S2 and containing Cu2+Solution mixes, with the pH of cushioning liquid regulation system extremely
Isothermal reaction 0.5-4h at 6,40-80 DEG C, filtering, filter cake is washed with deionized into filtrate Cu2+<0.05mg/L, dries, and grinds
Mill, obtains powdered containing carbon/carbon-copper composite material；
S4. it is calcined:In parts by weight, by 60-80 parts of S3 containing carbon/carbon-copper composite material, 10-20 parts of powdered biological
Material (particle diameter is less than 200 mesh), 5-10 parts of adhesive and 10-20 parts of water are uniformly mixed, then in forging at 150-400 DEG C
2-4h is burnt, room temperature is cooled under oxygen-free environment, obtain final product the adsorption sustained-release filler for artificial swamp.
Specifically, the matrix material in S1 is any one in montmorillonite, kaolin and attapulgite or any various
Mixing.
Specifically, the acid solution in S1 and S2 is hydrochloric acid, sulfuric acid or nitric acid, its concentration is 0.5-4mol/L.
Specifically, activated matrix material and the mass ratio of water are 1 in slurries in S2：(5~10), the volume of acid solution in S2
It is the 1-5% of slurry volume.
Specifically, aniline and the mass ratio of activated matrix material are 0.1-1 in S2：1, aniline is with the mass ratio of initiator
1：0.001-0.01.
Specifically, in S3 containing Cu2+Cu in solution2+Concentration be 50-800mg/L, in S3 overlay film matrix material with contain Cu2 +The amount ratio of solution is 30-60g:250mL.
Specifically, the cushioning liquid in S3 is NaAC-HAC cushioning liquid.
Specifically, biological material in S4 be rice straw, maize straw, wheat stalk, rice husk, wheat shell, wood chip,
Any one in paper scrap and corncob or any various mixing.
Specifically, adhesive in S4 for clay or by magnesia, calgon, water, Ludox constitute it is compound viscous
Mixture.
The present invention also provides a kind of adsorption sustained-release filler for artificial swamp, and it passes through the above method and prepares.
Compared with prior art, the beneficial effects of the invention are as follows：
1) adsorbance of the adsorption sustained-release filler that the present invention is provided is big, high adsorption capacity, when the pollutant such as nitrogen phosphorus in water inlet
Because content is more cannot be complete by the plant absorption on artificial swamp top layer when, the adsorption sustained-release filler can be to the pollutant that has more
Effectively adsorbed, so that the water outlet after artificial wetland treatment meets requirement up to standard；
2) the adsorption sustained-release filler that the present invention is provided has slow-release capability, and when water inlet, the pollutant such as nitrogen phosphorus contains less or in water inlet
When cannot meet the plant growth on artificial swamp top layer when measuring low, the nitrogen phosphorus that the adsorption sustained-release filler will can be adsorbed before in it
Slowly discharged in the very low water body of nitrogen and phosphorus content at root system of plant Deng material, to meet the growth demand of plant, in summary
Using after the adsorption sustained-release filler that the present invention is provided, artificial swamp bears external environment change (in inflow size variation, water inlet
Dirt content how much change etc.) ability it is stronger；
3) it is montmorillonite, kaolin and attapulgite and biological material etc. to prepare the primary raw material of the adsorption sustained-release material
Cheap products, therefore its production cost is relatively low.
Specific embodiment
Principle of the invention and feature are described below in conjunction with specific embodiment, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1
S1. activate：By particle diameter in the montmorillonite matrix material input reactor of 200-2000 mesh and with 0.5mol/L's
Hydrochloric acid solution is submerged, stir-activating 12h, and centrifugation is simultaneously washed to neutrality, is dried, and obtains final product activated matrix material, standby；
S2. overlay film：Activated matrix material 50g in S1 is mixed with 250mL water, slurries are beaten to obtain, 0.5mol/L is added
Hydrochloric acid solution 12.5mL, sequentially add 5g aniline and 0.05g initiators, stirring at normal temperature reaction 2h, suction filtration, washing, drying,
Grinding, sieving, obtain final product overlay film matrix material, and its particle diameter is 200-2000 mesh；
S3. it is combined：By the overlay film matrix material 30g in S2 and containing Cu2+The solution 250mL mixing of 50mg/L, uses NaAC-
To 6, isothermal reaction 4h at 40 DEG C, filtering, filter cake is washed with deionized to Cu the pH of HAC cushioning liquid regulation systems2+Content
Less than 0.05mg/L, dry, grinding obtains powdered containing carbon/carbon-copper composite material, and its particle diameter (is equal to or less than 200 mesh below 200 mesh
The particle diameter of particle)；
S4. it is calcined:In parts by weight, by 60 parts of S3 containing carbon/carbon-copper composite material, (particle diameter is less than 10 parts of maize straws
200 mesh), 5 parts of clays and 10 parts of water be uniformly mixed, be then cooled to room temperature under 4h, oxygen-free environment is calcined at 150 DEG C,
Obtain final product the adsorption sustained-release filler for artificial swamp.
Embodiment 2
S1. activate：By particle diameter in the kaolin matrix material input reactor of 200-2000 mesh and with the salt of 4mol/L
Acid solution is submerged, stir-activating 1h, and centrifugation is simultaneously washed to neutrality, is dried, and obtains final product activated matrix material, standby；
S2. overlay film：Activated matrix material 50g in S1 is mixed with 500mL water, slurries are beaten to obtain, adds 4mol/L's
Hydrochloric acid solution 25mL, sequentially adds 50g aniline and 0.05g initiators, stirring at normal temperature reaction 2-8h, suction filtration, washing, drying,
Grinding, sieving, obtain final product overlay film matrix material, and its particle diameter is 200-2000 mesh；
S3. it is combined：By the overlay film matrix material 45g in S2 and containing Cu2+The solution 250mL mixing of 800mg/L, uses NaAC-
To 6, isothermal reaction 2h at 60 DEG C, filtering, filter cake is washed with deionized to Cu the pH of HAC cushioning liquid regulation systems2+Content
Less than 0.05mg/L, dry, grinding obtains powdered containing carbon/carbon-copper composite material, and its particle diameter is below 200 mesh；
S4. it is calcined:In parts by weight, by 70 parts of S3 containing carbon/carbon-copper composite material, (particle diameter is less than 15 parts of wheat shells
200 mesh), 7 parts of clays and 15 parts of water be uniformly mixed, be then cooled to room temperature under 3h, oxygen-free environment is calcined at 260 DEG C,
Obtain final product the adsorption sustained-release filler for artificial swamp.
Embodiment 3
S1. activate：By particle diameter in the attapulgite matrix material input reactor of 200-2000 mesh and with 2mol/L's
Hydrochloric acid solution is submerged, stir-activating 6h, and centrifugation is simultaneously washed to neutrality, is dried, and obtains final product activated matrix material, standby；
S2. overlay film：Activated matrix material 50g in S1 is mixed with 400mL water, slurries are beaten to obtain, adds 2mol/L's
Hydrochloric acid solution 18mL, sequentially adds 25g aniline and 0.025g initiators, stirring at normal temperature reaction 2-8h, suction filtration, washing, drying,
Grinding, sieving, obtain final product overlay film matrix material, and its particle diameter is 200-2000 mesh；
S3. it is combined：By the overlay film matrix material 60g in S2 and containing Cu2+The solution 250mL mixing of 300mg/L, uses NaAC-
To 6, isothermal reaction 0.5h at 80 DEG C, filtering, filter cake is washed with deionized to Cu the pH of HAC cushioning liquid regulation systems2+Contain
Amount is less than 0.05mg/L, dries, and grinding obtains powdered containing carbon/carbon-copper composite material, and its particle diameter is below 200 mesh；
S4. it is calcined:In parts by weight, by 80 parts of S3 containing carbon/carbon-copper composite material, (particle diameter is less than 20 parts of rice straws
200 mesh), 10 parts of clays and 20 parts of water be uniformly mixed, be then cooled to room temperature under 4h, oxygen-free environment is calcined at 150 DEG C,
Obtain final product the adsorption sustained-release filler for artificial swamp.
Absorption property is detected：
The adsorption sustained-release material that will be prepared by above method is used in urban wastewater treatment, modified montmorillonite,
Kaolin and attapulgite are corresponding in turn to the adsorption sustained-release filler that embodiment 1 to 3 is prepared, and with montmorillonite before modified,
Kaolin, attapulgite absorption property are contrasted, to same sewage by after the adsorption treatment of same time period, to nitrogen
(referring mainly to ammonia nitrogen), the adsorbance of phosphorus are tested, and test result is as shown in the table：
Knowable to the data in upper table, the adsorption sustained-release filler for artificial swamp prepared by the present invention is to the nitrogen in sewage
There is stronger adsorption capacity with phosphorus.
Sustained release performance is detected：
The adsorption sustained-release material that will be prepared by above method is used in urban wastewater treatment, modified montmorillonite,
Kaolin and attapulgite are corresponding in turn to the adsorption sustained-release filler that embodiment 1 to 3 is prepared.Normally run in wet land system
Afterwards, during the autumn and winter plant harvesting phase, the removal of nitrogen phosphorus takes Partial Wetland and fills out mainly by the suction-operated of wet land filler in water inlet
Material, is parsed to the ammonia nitrogen in filler, phosphorus, is determined, and taken the water outlet in the period simultaneously and be measured.
After above-mentioned autumn and winter plant harvesting, wet season summer is waited until, because water is big, therefore nitrogen phosphorus concentration in water inlet
Relatively low (the NH of content3-N<8mg/L, P<1.0mg/L), the nitrogen phosphorus in water is not enough to allow the more preferable of plant growth, and now filler starts
At the end of the nitrogen phosphorus that slow release absorbs supplies plant growth, wet season fast, take Partial Wetland filler, to the nitrogen in adsorption stuffing,
Phosphorus is parsed, determined, and is taken the water outlet in the period simultaneously and be measured, and the result after measure see the table below：
Data in analysis upper table understand that the wet season is big because of water, therefore nitrogen, phosphorus equal size are relatively fewer in water inlet, but should
Plant growth is fast during season, therefore nitrogen phosphorus can be fully absorbed and still had some deficits in water inlet, therefore nitrogen phosphorus contains in the water on filler top
Amount is considerably less, and now filler will can slowly discharge in the nitrogen phosphorus of other periods such as harvest time absorption before it to its upper area,
For plant absorption.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. the preparation method of a kind of adsorption sustained-release filler for artificial swamp, it is characterised in that comprise the following steps：
S1. activate：To be submerged in matrix material input reactor after screening and with acid solution, stir-activating 1-12h, from
The heart is separated and is washed to neutrality, is dried, and obtains final product activated matrix material, standby；
S2. overlay film：Activated matrix material in S1 is mixed with water, slurries are beaten to obtain, acid solution is added, aniline is sequentially added
And initiator, stirring at normal temperature reaction 2-8h, suction filtration, washing, drying, grinding, sieving obtain final product overlay film matrix material；
S3. it is combined：By the overlay film matrix material in S2 and containing Cu2+Solution mixes, with the pH to 6,40- of cushioning liquid regulation system
Isothermal reaction 0.5-4h at 80 DEG C, filtering, filter cake is washed with deionized the Cu into washing filtrate2+Content is less than 0.05mg/L,
Dry, grinding obtains powdered containing carbon/carbon-copper composite material；
S4. it is calcined:In parts by weight, by 60-80 parts of S3 containing carbon/carbon-copper composite material, 10-20 parts of biological material, 5-10
Part adhesive and 10-20 parts of water are uniformly mixed, and are then cooled to room under 2-4h, oxygen-free environment is calcined at 150-400 DEG C
Temperature, obtains final product the adsorption sustained-release filler for artificial swamp.
2. the preparation method of a kind of adsorption sustained-release filler for artificial swamp according to claim 1, it is characterised in that
Matrix material in S1 is any one in montmorillonite, kaolin and attapulgite or any various mixing.
3. the preparation method of a kind of adsorption sustained-release filler for artificial swamp according to claim 1, it is characterised in that
Acid solution in S1 and S2 is hydrochloric acid, sulfuric acid or nitric acid, and its concentration is 0.5-4mol/L.
4. the preparation method of a kind of adsorption sustained-release filler for artificial swamp according to claim 1, it is characterised in that
Activated matrix material and the mass ratio of water are 1 in slurries in S2：(5~10), the volume of acid solution is the 1- of slurry volume in S2
5%.
5. the preparation method of a kind of adsorption sustained-release filler for artificial swamp according to claim 1, it is characterised in that
Aniline and the mass ratio of activated matrix material are 0.1-1 in S2：1, aniline is 1 with the mass ratio of initiator：0.001-0.01, institute
It is one or more in sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate to state initiator.
6. the preparation method of a kind of adsorption sustained-release filler for artificial swamp according to claim 1, it is characterised in that
In S3 containing Cu2+Cu in solution2+Concentration be 50-800mg/L, in S3 overlay film matrix material with contain Cu2+The amount ratio of solution is
30-60g:250mL。
7. the preparation method of a kind of adsorption sustained-release filler for artificial swamp according to claim 1, it is characterised in that
Cushioning liquid in S3 is NaAC-HAC cushioning liquid.
8. the preparation method of a kind of adsorption sustained-release filler for artificial swamp according to claim 1, it is characterised in that
Biological material in S4 is in rice straw, maize straw, wheat stalk, rice husk, wheat shell, wood chip, paper scrap and corncob
Any one or any various mixing.
9. the preparation method of a kind of adsorption sustained-release filler for artificial swamp according to any one of claim 1 to 8, its
It is characterised by, the adhesive in S4 is clay or the composite adhesive being made up of magnesia, calgon, water, Ludox.
10. a kind of adsorption sustained-release filler for artificial swamp, it is characterised in that by described in any one of claim 1 to 9
Method is prepared.
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| CN110357198A (en) * | 2019-06-11 | 2019-10-22 | 武汉兴天宇环境股份有限公司 | A kind of adsorbent material and preparation method thereof for Low Concentration Ammonia Containing Wastewater processing |
| CN115465943A (en) * | 2022-09-21 | 2022-12-13 | 王卓 | Constructed wetland nitrogen and phosphorus removal filler with slow-release carbon material and preparation method thereof |
| CN116119833A (en) * | 2022-11-29 | 2023-05-16 | 嘉兴沃特泰科环保科技股份有限公司 | Nutrient for water recovery system and preparation method and application thereof |
| CN116119833B (en) * | 2022-11-29 | 2023-09-08 | 嘉兴沃特泰科环保科技股份有限公司 | Nutrient for water recovery system and preparation method and application thereof |
| CN116409880A (en) * | 2023-03-06 | 2023-07-11 | 商洛学院 | Preparation method for preparing high-performance constructed wetland filler by using tailings |
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| CN106669606B (en) | 2019-06-18 |
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Denomination of invention: An adsorption slow-release filler for constructed wetland and its preparation method Effective date of registration: 20230303 Granted publication date: 20190618 Pledgee: Bank of China Limited Wuhan Hanyang sub branch Pledgor: WUHAN FUND ENVIRONMENT PROTECTION Co.,Ltd. Registration number: Y2023420000088 |
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