CN111203183A - Preparation method of chemically grafted and modified biomass adsorbent - Google Patents
Preparation method of chemically grafted and modified biomass adsorbent Download PDFInfo
- Publication number
- CN111203183A CN111203183A CN202010053211.7A CN202010053211A CN111203183A CN 111203183 A CN111203183 A CN 111203183A CN 202010053211 A CN202010053211 A CN 202010053211A CN 111203183 A CN111203183 A CN 111203183A
- Authority
- CN
- China
- Prior art keywords
- biomass
- modified
- adsorbent
- preparation
- solution
- 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.)
- Pending
Links
Images
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
- 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
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic 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)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a chemically grafted and modified biomass adsorbent, relates to a preparation method of a biomass adsorbent, and aims to solve the problem that the existing cellulose-rich biomass adsorbent is weak in adsorption capacity to metal ions. The preparation method comprises the following steps: firstly, carrying out pyrolysis treatment on a biomass material by adopting an oxygen-limited heating carbonization method to obtain carbonized biomass; secondly, adding the carbonized biomass into a trichloromethane solution of pyridine, dropwise adding 4-bromobutyryl chloride, sealing the reaction mixed solution, and carrying out oscillation reaction; and thirdly, mixing the polyethyleneimine, KOH and tert-amyl alcohol to obtain a mixed modified solution, immersing the cleaned biomass into the mixed modified solution, and carrying out oscillation reaction at the temperature of 70-80 ℃ to obtain the chemically grafted and modified biomass adsorbent. The invention prepares the novel efficient environment-friendly modified biomass adsorbent by combining physical and chemical activation and modifying through carbonization and graft copolymerization.
Description
Technical Field
The invention relates to a preparation method of a biomass adsorbent.
Background
In recent years, research on the utilization of agricultural wastes to modify cellulose adsorbents for adsorbing, separating and extracting heavy metal ions in wastewater has been carried out, and compared with a common heavy metal treatment method, the method has the advantages of large adsorption capacity, high adsorption speed, low cost, simplicity in operation, no secondary pollution and the like. Therefore, research on this aspect has become a hotspot in this field. The agricultural wastes are wide in source, the main chemical components of the agricultural wastes are cellulose, hemicellulose and lignin, and the agricultural wastes have good biodegradability and certain adsorption performance and become one of the most promising materials at present. Cellulose-rich crop wastes have become an alternative low value adsorbent in the treatment of heavy metal ion pollution. Hydroxyl groups on cellulose are effective groups for removing metal ions, but the hydroxyl groups cannot effectively improve the adsorption capacity and adsorption selectivity of the cellulose to the metal ions. How to make the crop waste become the environment-friendly high-efficiency adsorbent becomes the mainstream of preparing the adsorbent at present.
Disclosure of Invention
The invention aims to solve the problem that the existing biomass adsorbent rich in cellulose has weak adsorption capacity on metal ions, and provides a preparation method of a biomass adsorbent modified by chemical grafting.
The preparation method of the chemically grafted and modified biomass adsorbent is realized according to the following steps:
firstly, carrying out pyrolysis treatment on a biomass material at 350-600 ℃ by adopting an oxygen-limited heating carbonization method to obtain a biochar adsorbent, and crushing the biochar adsorbent after natural cooling to obtain carbonized biomass;
secondly, adding the carbonized biomass into a trichloromethane solution of pyridine, dropwise adding 4-bromobutyryl chloride, sealing the reaction mixed solution, carrying out oscillation reaction for 10-16 h, filtering, and washing with trichloromethane to obtain the cleaned biomass;
and thirdly, mixing polyethyleneimine, KOH and tert-amyl alcohol to obtain a mixed modified solution, immersing the cleaned biomass into the mixed modified solution, carrying out oscillation reaction at the temperature of 70-80 ℃, cleaning, and drying to obtain the chemically grafted and modified biomass adsorbent.
The biomass adsorbent modified by chemical grafting prepared by the invention has great advantages in heavy metal adsorption, and is mainly embodied in the following aspects:
(1) the biochar has a loose and porous structure, large specific surface area, high porosity, large total pore volume and high specific surface energy, and provides more effective sites for heavy metal adsorption;
(2) the surface of the biochar contains various functional groups such as hydroxyl, carboxyl, amino and the like; and may contain mineral components such as P, etc. for promoting adsorption efficiency;
(3) the integral structure of the biochar is highly aromatic, has higher stability and is not easy to be oxidized, so that the problem that other adsorption materials are easy to be oxidized in the reaction process is solved;
(4) the surface of the biochar has more negative charges, so that the Cation Exchange Capacity (CEC) of the biochar is larger, and heavy metal ions are generally positively charged, so that the electrostatic attraction between the biochar and the heavy metal ions is enhanced, and the biochar shows good adsorption characteristics.
The synthesis of the cellulose graft copolymer in the biomass adsorbent is mostly free radical polymerization, namely, free radical chain polymerization with single electron is adopted as an active monomer. The reaction process is that free radicals are formed on free hydroxyl groups on D-hexacyclic glucose group (after ring breaking), and chain reaction is carried out on the free radicals and a grafting monomer, so that a new functional branched chain is introduced, and the adsorption effect on heavy metals is increased.
The invention prepares the novel efficient environment-friendly modified biomass adsorbent by combining physical and chemical activation and modifying through carbonization and graft copolymerization.
Drawings
Fig. 1 is an electron microscope image of a biomass adsorbent chemically grafted and modified according to the first preparation example.
Detailed Description
The first embodiment is as follows: the preparation method of the chemically grafted and modified biomass adsorbent is implemented according to the following steps:
firstly, carrying out pyrolysis treatment on a biomass material at 350-600 ℃ by adopting an oxygen-limited heating carbonization method to obtain a biochar adsorbent, and crushing the biochar adsorbent after natural cooling to obtain carbonized biomass;
secondly, adding the carbonized biomass into a trichloromethane solution of pyridine, dropwise adding 4-bromobutyryl chloride, sealing the reaction mixed solution, carrying out oscillation reaction for 10-16 h, filtering, and washing with trichloromethane to obtain the cleaned biomass;
and thirdly, mixing polyethyleneimine, KOH and tert-amyl alcohol to obtain a mixed modified solution, immersing the cleaned biomass into the mixed modified solution, carrying out oscillation reaction at the temperature of 70-80 ℃, cleaning, and drying to obtain the chemically grafted and modified biomass adsorbent.
The embodiment can change the physical or chemical characteristics of the surface of the reaction substrate through graft polymerization, and the adsorption performance of the crop wastes can be improved by introducing specific functional groups on the surface through carbonization and graft polymerization reactions, so that the efficient adsorbent based on the agricultural wastes is prepared.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the oxygen-limited temperature-rising carbonization method in the first step is to heat the biomass material to 350-600 ℃ at a speed of 10 ℃/min under the anoxic (oxygen-free) condition, and then to carry out the pyrolysis treatment.
The third concrete implementation mode: the difference between the first embodiment and the second embodiment is that the biomass material in the first step is mushroom bran, corn straw, rice hull or hemp.
The fourth concrete implementation mode: the difference between the first embodiment and the first to third embodiments is that the biomass material is pyrolyzed at 350-600 ℃ for 3.5-4.5 h.
The fifth concrete implementation mode: the present embodiment is different from the first to fourth embodiments in that the particle size of the biomass carbonized in the first step is 0.2mm to 0.3 mm.
The sixth specific implementation mode: this embodiment is different from the first to fifth embodiments in that the molar ratio of pyridine to 4-bromobutyryl chloride in the second step is 6 to 8: 10.
The seventh embodiment: the embodiment is different from the first to sixth embodiments in that the molar ratio of the polyethyleneimine to the 4-bromobutyryl chloride in the mixed modification solution in the third step is 280-320: 1.
The specific implementation mode is eight: the difference between the present embodiment and one of the first to seventh embodiments is that the third step is performed with shaking reaction at a temperature of 70-80 ℃ for 20-30 h.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is that the cleaning in the third step is performed by sequentially using methanol and deionized water.
The first embodiment is as follows: the preparation method of the biomass adsorbent modified by chemical grafting is implemented according to the following steps:
firstly, an oxygen-limited heating carbonization method is adopted, namely, under the anoxic condition, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min, the hemp stalk biomass material is subjected to pyrolysis treatment for 4 hours to obtain a charcoal adsorbent, the charcoal adsorbent is naturally cooled, crushed to 0.25mm (60 meshes), and placed in a sealing bag for sealing and storage to obtain carbonized biomass;
adding 10g of carbonized biomass into a mixed solution of 2.5mL of pyridine and 95mL of trichloromethane, dropwise adding 5mL of 4-bromobutyryl chloride, sealing the reaction mixed solution, carrying out slow oscillation reaction at 25 ℃ for 12h, filtering, washing with trichloromethane to wash away unreacted 4-bromobutyryl chloride, and thus obtaining a washed biomass;
and thirdly, mixing 10g of polyethyleneimine, 0.1g of KOH and 90mL of tertiary amyl alcohol to obtain a mixed modified solution, immersing the cleaned biomass into the mixed modified solution, carrying out oscillation reaction at the temperature of 75 ℃ for 24 hours, cleaning with excessive methanol and deionized water, and drying to constant weight to obtain the chemical grafting modified biomass adsorbent.
Taking 100ml of Cd-containing solution (4.47mg/L), respectively adding 0.01g, 0.02g, 0.03g, 0.04g and 0.05g of the biomass adsorbent chemically grafted and modified by the embodiment into the Cd-containing solution, and reacting for 2 hours, wherein the adsorption rates are 87.96%, 91.38%, 94.22%, 95.81% and 96.30%.
The biomass adsorbent modified by chemical grafting obtained in the embodiment has high adsorption capacity and adsorption selectivity to metal ions.
Example two: the difference between the first embodiment and the second embodiment is that in the first step, an oxygen-limited temperature-rising carbonization method is adopted, namely, the temperature is raised to 350 ℃ at a temperature-rising rate of 10 ℃/min under an anoxic condition, and the hemp stalk biomass material is subjected to pyrolysis treatment for 4 hours to obtain the charcoal adsorbent.
The biomass adsorbent modified by chemical grafting obtained in the example adsorbs a low-concentration Cd solution (<5mg/L), and the adsorption rate is 87.65%.
Example three: the difference between the first embodiment and the second embodiment is that in the first step, an oxygen-limited temperature-rising carbonization method is adopted, namely, the temperature is raised to 400 ℃ at a temperature-rising rate of 10 ℃/min under an anoxic condition, and the hemp stalk biomass material is subjected to pyrolysis treatment for 4 hours to obtain the charcoal adsorbent.
The biomass adsorbent (0.01g) chemically grafted and modified in the example adsorbs a low-concentration Cd solution (<5mg/L), and the adsorption rate is 92.19%.
Example four: the difference between the first embodiment and the second embodiment is that in the first step, an oxygen-limited temperature-rising carbonization method is adopted, namely, the temperature is raised to 450 ℃ at a temperature-rising rate of 10 ℃/min under an anoxic condition, and the hemp stalk biomass material is subjected to pyrolysis treatment for 4 hours to obtain the charcoal adsorbent.
The biomass adsorbent (0.01g) modified by chemical grafting obtained in the example adsorbs a low-concentration Cd solution (<5mg/L), and the adsorption rate is 93.47%.
Example five: the difference between the first embodiment and the second embodiment is that in the first step, an oxygen-limited temperature-rising carbonization method is adopted, namely, the temperature is raised to 600 ℃ at a temperature-rising rate of 10 ℃/min under an anoxic condition, and the hemp stalk biomass material is subjected to pyrolysis treatment for 4 hours to obtain the charcoal adsorbent.
The biomass adsorbent (0.01g) modified by chemical grafting obtained in the example adsorbs a low-concentration Cd solution (<5mg/L), and the adsorption rate is 96.30%.
Claims (9)
1. The preparation method of the biomass adsorbent modified by chemical grafting is characterized by comprising the following steps:
firstly, carrying out pyrolysis treatment on a biomass material at 350-600 ℃ by adopting an oxygen-limited heating carbonization method to obtain a biochar adsorbent, and crushing the biochar adsorbent after natural cooling to obtain carbonized biomass;
secondly, adding the carbonized biomass into a trichloromethane solution of pyridine, dropwise adding 4-bromobutyryl chloride, sealing the reaction mixed solution, carrying out oscillation reaction for 10-16 h, filtering, and washing with trichloromethane to obtain the cleaned biomass;
and thirdly, mixing polyethyleneimine, KOH and tert-amyl alcohol to obtain a mixed modified solution, immersing the cleaned biomass into the mixed modified solution, carrying out oscillation reaction at the temperature of 70-80 ℃, cleaning, and drying to obtain the chemically grafted and modified biomass adsorbent.
2. The method for preparing the biomass adsorbent modified by chemical grafting according to claim 1, wherein the oxygen-limited temperature-rising carbonization method in the first step is to heat the biomass material to 350-600 ℃ at a speed of 10 ℃/min under the anoxic condition.
3. The method for preparing the biomass adsorbent modified by chemical grafting according to claim 1, wherein the biomass material in the first step is mushroom bran, corn straw, rice hull or hemp.
4. The method for preparing the biomass adsorbent modified by chemical grafting according to claim 1, wherein the biomass material is subjected to pyrolysis treatment at 350-600 ℃ for 3.5-4.5 h.
5. The method for preparing the biomass adsorbent modified by chemical grafting according to claim 1, wherein the particle size of the biomass after carbonization in the first step is 0.2mm to 0.3 mm.
6. The preparation method of the biomass adsorbent modified by chemical grafting according to claim 1, wherein the molar ratio of the pyridine to the 4-bromobutyryl chloride in the second step is 6-8: 10.
7. The preparation method of the biomass adsorbent modified by chemical grafting according to claim 1, wherein the molar ratio of polyethyleneimine to 4-bromobutyryl chloride in the mixed modification solution in the third step is 280-320: 1.
8. The preparation method of the biomass adsorbent modified by chemical grafting according to claim 1, wherein the third step is carried out for 20-30 h at 70-80 ℃ by oscillation reaction.
9. The method for preparing the biomass adsorbent modified by chemical grafting according to claim 1, wherein the washing in the third step is sequentially carried out by using methanol and deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010053211.7A CN111203183A (en) | 2020-01-17 | 2020-01-17 | Preparation method of chemically grafted and modified biomass adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010053211.7A CN111203183A (en) | 2020-01-17 | 2020-01-17 | Preparation method of chemically grafted and modified biomass adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111203183A true CN111203183A (en) | 2020-05-29 |
Family
ID=70782105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010053211.7A Pending CN111203183A (en) | 2020-01-17 | 2020-01-17 | Preparation method of chemically grafted and modified biomass adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111203183A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547015A (en) * | 2020-12-07 | 2021-03-26 | 西安工业大学 | Preparation method and application of PEI modified biochar |
| CN113289584A (en) * | 2021-07-05 | 2021-08-24 | 黑龙江省科学院高技术研究院 | Preparation method and application of sunflower straw charcoal adsorbent |
| CN114982547A (en) * | 2022-07-13 | 2022-09-02 | 安徽农业大学 | Camellia oleifera cultivation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816920A (en) * | 2010-03-25 | 2010-09-01 | 湖南大学 | Modified phanerochaete chrysosporium adsorbent as well as preparation and application thereof |
| CN104759268A (en) * | 2015-04-15 | 2015-07-08 | 长沙学院 | Preparation method of ACF/GO/PEI composite material capable of efficiently adsorbing heavy metal |
| CN104944596A (en) * | 2015-06-08 | 2015-09-30 | 黑龙江省科学院高技术研究院 | Method for treating hexavalent chromium wastewater by aspergillus niger spore |
| CN106111065A (en) * | 2016-07-01 | 2016-11-16 | 昆明理工大学 | A kind of modified activated carbon absorbent and its preparation method and application |
| CN108499544A (en) * | 2018-03-27 | 2018-09-07 | 广西大学 | A kind of preparation method of polystyrene microsphere fiber type element base weight metal absorbent |
-
2020
- 2020-01-17 CN CN202010053211.7A patent/CN111203183A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816920A (en) * | 2010-03-25 | 2010-09-01 | 湖南大学 | Modified phanerochaete chrysosporium adsorbent as well as preparation and application thereof |
| CN104759268A (en) * | 2015-04-15 | 2015-07-08 | 长沙学院 | Preparation method of ACF/GO/PEI composite material capable of efficiently adsorbing heavy metal |
| CN104944596A (en) * | 2015-06-08 | 2015-09-30 | 黑龙江省科学院高技术研究院 | Method for treating hexavalent chromium wastewater by aspergillus niger spore |
| CN106111065A (en) * | 2016-07-01 | 2016-11-16 | 昆明理工大学 | A kind of modified activated carbon absorbent and its preparation method and application |
| CN108499544A (en) * | 2018-03-27 | 2018-09-07 | 广西大学 | A kind of preparation method of polystyrene microsphere fiber type element base weight metal absorbent |
Non-Patent Citations (1)
| Title |
|---|
| 李力等: ""玉米秸秆生物炭对 Cd（Ⅱ）的吸附机理研究"", 《农业环境科学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547015A (en) * | 2020-12-07 | 2021-03-26 | 西安工业大学 | Preparation method and application of PEI modified biochar |
| CN113289584A (en) * | 2021-07-05 | 2021-08-24 | 黑龙江省科学院高技术研究院 | Preparation method and application of sunflower straw charcoal adsorbent |
| CN114982547A (en) * | 2022-07-13 | 2022-09-02 | 安徽农业大学 | Camellia oleifera cultivation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111203183A (en) | Preparation method of chemically grafted and modified biomass adsorbent | |
| Senthil et al. | Biomass-derived biochar materials as sustainable energy sources for electrochemical energy storage devices | |
| Zhou et al. | Upgrading earth-abundant biomass into three-dimensional carbon materials for energy and environmental applications | |
| CN111017927A (en) | Preparation and application method of nitrogen-doped porous carbon based on straw hydrothermal carbonization | |
| JP2003147643A (en) | Carbon fiber form produced by vapor growth method | |
| CN114307964B (en) | Method for preparing iron-nitrogen-doped biochar functional material based on waste paper box and application | |
| CN107697913B (en) | Preparation method of walnut shell-based high-capacitance graded porous carbon | |
| KR102331277B1 (en) | Polymer-modified silicon-carbon composite and use thereof | |
| CN112420402A (en) | Nitrogen-doped biochar, preparation method and application thereof, electrode and preparation method | |
| CN108615888B (en) | Biomass carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof | |
| CN110422843A (en) | A kind of environment-friendly preparation method thereof of the biomass-based active carbon material of nitrogen boron codope and its application | |
| CN108923047B (en) | Hollow carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof | |
| CN110201636B (en) | Preparation method of modified biochar | |
| CN104300124A (en) | Preparation method for silicon dioxide/carbon compound and application to lithium/sodium ion batteries | |
| CN112374544A (en) | Super capacitor electrode material and preparation method thereof | |
| CN110745974B (en) | Harmless treatment method for kitchen waste | |
| CN112194132A (en) | Preparation method and application of iron-modified carbon microsphere/carbon nanosheet composite porous carbon based on moso bamboo hydrothermal carbonization | |
| CN111530436A (en) | Method for modifying shells | |
| CN111889075A (en) | Activated carbon adsorbent prepared from papermaking sludge and preparation method and application thereof | |
| CN108745416B (en) | Preparation method of power generation-energy storage porous film loaded photocatalyst composite material | |
| CN113713766A (en) | Preparation method of biochar with excellent adsorption performance | |
| CN107815449B (en) | Preparation method of immobilized enzyme oil spill degradation agent | |
| CN107058427B (en) | Method for strengthening ammonia pretreatment of waste biomass by using lignin degrading bacteria | |
| CN108786857B (en) | Carbon dot/two-dimensional MoS2Composite photocatalyst and preparation method thereof | |
| CN112614995A (en) | FeS nanoflower in-situ doped porous carbon nanofiber negative electrode material and preparation method thereof |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210719 Address after: 150010 No.135, Nanma Road, Daowai District, Harbin City, Heilongjiang Province Applicant after: INSTITUTE OF ADVANCED TECHNOLOGY OF HEILONGJIANG ACADEMY OF SCIENCES Applicant after: Heilongjiang Aochi Environmental Protection Technology Co.,Ltd. Address before: 150010 No.135, Nanma Road, Daowai District, Harbin City, Heilongjiang Province Applicant before: INSTITUTE OF ADVANCED TECHNOLOGY OF HEILONGJIANG ACADEMY OF SCIENCES |
|
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200529 |