CN111138109A - Cotton stalk lignin-based air entraining agent and preparation method and application thereof - Google Patents
Cotton stalk lignin-based air entraining agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN111138109A CN111138109A CN201911366961.3A CN201911366961A CN111138109A CN 111138109 A CN111138109 A CN 111138109A CN 201911366961 A CN201911366961 A CN 201911366961A CN 111138109 A CN111138109 A CN 111138109A
- Authority
- CN
- China
- Prior art keywords
- cotton stalk
- air entraining
- entraining agent
- stalk lignin
- lignin
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/304—Air-entrainers
Abstract
The invention relates to the technical field of concrete admixtures, in particular to a cotton stalk lignin-based air entraining agent and a preparation method and application thereof, wherein the cotton stalk lignin-based air entraining agent comprises the following raw materials in parts by weight: mixing the three components, stirring uniformly to obtain a cotton stalk lignin mixed solution, and heating to obtain a reaction product; cooling the reaction product to room temperature, neutralizing the reaction product with hydrochloric acid solution, carrying out suction filtration, purifying the obtained suction filtration solution with anion-cation exchange resin, neutralizing the purified solution with sodium hydroxide solution to obtain the sodium cotton stalk lignin sulfonate, and carrying out vacuum drying to obtain the cotton stalk lignin-based air entraining agent. The invention fully utilizes the agricultural waste cotton stalks to produce the economical and environment-friendly concrete air entraining agent, has wide raw material sources, lower cost and environmental protection, and the cotton stalk lignin-based air entraining agent is used as the concrete admixture, can improve the air content to 5 to 10 percent and keeps the mechanical property unchanged.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, and discloses a cotton stalk lignin-based air entraining agent, and a preparation method and application thereof.
Background
Concrete is widely applied to buildings, bridges, roads and other projects, but most of the concrete projects fail before the designed service life of the concrete projects is reached, and the main reason is that in alpine climates, the concrete is affected by frequent freeze thawing, so that the material is cracked and damaged. The antifreezing property of the concrete is improved, the air entraining agent is most widely doped into the concrete at present, and the air entraining agent is an additive which can enable the concrete to generate a large amount of uniform, stable and closed micro-bubbles in the stirring process. The air bubbles can effectively improve the easy mixing property, frost resistance and impermeability of the concrete. The air entraining agent is doped in the concrete, so that the pore structure of the concrete can be improved, and the durability of the concrete is greatly improved.
The air entraining agent is a great invention in the building history, and the service life of the concrete outdoors is prolonged. Air entraining agents were invented in the 30's of the 20 th century, when aimed at increasing road ages in north america. North American climate is cold, the pavement is exposed to cold and humid environments for a long time, and anti-icing salt is sprinkled every winter, resulting in cracking of the pavement. It was found that the concrete containing rosin resin had bubbles inside, resulting in better durability. Thereafter, the air entraining agent is started to be popularized and used in the united states. In 1942, the air entraining concrete engineering specification is firstly made in the United states, and then the air entraining agent is widely used in the projects such as highways, dams, bridges and the like. The attention of China on air entraining agents is greatly improved in recent years, and the air entraining agents are mixed in large concrete projects such as Qinghai-Tibet railway which is in dynamic operation in 1958, Guzhou dam hydro junction engineering which is in dynamic operation in 1974, Sanxia hydro junction engineering which is in dynamic operation in 1994 and the like. The air entraining agent is added to effectively improve the workability of conventional concrete and special concrete with high flow state, abrasion resistance, steel fiber, pumping and the like in main engineering, reduce the segregation of the concrete, improve the impermeability and frost resistance of the concrete, meet the durability requirement of mass concrete and obtain good social and economic benefits. The air entraining agents on the market in China are mainly divided into rosin resins, alkyl benzene sulfonates, fatty alcohols, gleditsin glycosides and lignosulphonates. These air entraining agents are not very effective and are expensive. The traditional lignosulfonate is extracted from papermaking waste liquid, has low purity and poor surface activity, and the produced sodium lignosulfonate air entraining agent has poor effect.
Cotton is one of the world's important crops, and cotton stalks are the major by-products in the cotton industry chain. The cotton stalk is used as an important wood fiber biomass resource, and has higher development value and wide development space. The cotton yield of China is the first in the world, and the quantity of cotton straw resources which can be collected by China every year exceeds 2500 million tons, so that the cotton is an inexhaustible bio-based renewable resource. The cotton stalks are converted into products with high added value, so that the income of farmers can be increased, the problems of pollution and plant diseases and insect pests caused by straw burning and returning are solved, the development of agriculture and rural areas in China is promoted, and the social and economic flourishing development in China is guaranteed. Lignin is a natural high molecular compound which is second to cellulose in nature and has the most abundant and unique aromatic structure, and accounts for about 15 to 20 percent of plant components in cotton straws. The lignin has active groups such as aromatic group, phenolic hydroxyl group, alcoholic hydroxyl group, carbonyl group, methoxyl group, carboxyl group, conjugated double bond and the like in a molecular structure, wherein the phenolic hydroxyl group and the alcoholic hydroxyl group have reactivity, caking property and oxidation resistance, and can replace fossil resources to be applied to the fields of resin material synthetic raw materials, plastic additives, concrete admixtures and the like.
Disclosure of Invention
The invention provides a cotton stalk lignin-based air entraining agent, a preparation method and application thereof, overcomes the defects of the prior art, and can effectively solve the problems of low purity and poor air entraining effect of the existing lignin-based air entraining agent.
One of the technical schemes of the invention is realized by the following measures: the cotton stalk lignin-based air entraining agent comprises, by weight, 5 parts of cotton stalk lignin, 1 to 10 parts of sodium sulfite and 50 to 100 parts of sodium hydroxide solution.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the preparation method comprises the following steps: firstly, mixing required amount of cotton stalk lignin, sodium sulfite and 50-100 parts of sodium hydroxide solution, and uniformly stirring to obtain a cotton stalk lignin mixed solution; secondly, heating the cotton stalk lignin mixed solution to 130-170 ℃ for reaction for 3-7 hours to obtain a reaction product; thirdly, cooling the reaction product to room temperature, neutralizing the reaction product with hydrochloric acid solution until the pH value of the reaction product is 7, carrying out suction filtration, purifying the obtained suction filtration liquid with anion-cation exchange resin, and neutralizing the purified liquid with sodium hydroxide solution until the pH value of the purified liquid is 7 to obtain the sodium lignosulfonate cotton stalk; fourthly, drying the cotton stalk lignin sodium sulfonate in vacuum at the temperature of 65-75 ℃ and under the pressure of-0.09 MPa to obtain the cotton stalk lignin-based air entraining agent.
The concentration of the hydrochloric acid solution is 1 mol/L.
The concentration of the sodium hydroxide solution was 1 mol/L.
The second technical scheme of the invention is realized by the following measures: a preparation method of a cotton stalk lignin-based air entraining agent comprises the following steps: firstly, mixing required amount of cotton stalk lignin, sodium sulfite and 50-100 parts of sodium hydroxide solution, and uniformly stirring to obtain a cotton stalk lignin mixed solution; secondly, heating the cotton stalk lignin mixed solution to 130-170 ℃ for reaction for 3-7 hours to obtain a reaction product; thirdly, cooling the reaction product to room temperature, neutralizing the reaction product with hydrochloric acid solution until the pH value of the reaction product is 7, carrying out suction filtration, purifying the obtained suction filtration liquid with anion-cation exchange resin, and neutralizing the purified liquid with sodium hydroxide solution until the pH value of the purified liquid is 7 to obtain the sodium lignosulfonate cotton stalk; fourthly, drying the cotton stalk lignin sodium sulfonate in vacuum at the temperature of 65-75 ℃ and under the pressure of-0.09 MPa to obtain the cotton stalk lignin-based air entraining agent.
The following is further optimization or/and improvement of the second technical scheme of the invention:
the concentration of the hydrochloric acid solution is 1 mol/L.
The concentration of the sodium hydroxide solution was 1 mol/L.
The third technical scheme of the invention is realized by the following measures: an application of cotton stalk lignin-based air entraining agent in concrete admixture.
The invention fully utilizes the agricultural waste cotton stalks to produce the economical and environment-friendly concrete air entraining agent, has wide raw material sources, lower cost and environmental protection, and the cotton stalk lignin-based air entraining agent is used as the concrete admixture, can improve the air content to 5 to 10 percent and keeps the mechanical property unchanged.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the cotton stalk lignin-based air entraining agent comprises, by weight, 5 parts of cotton stalk lignin, 1 to 10 parts of sodium sulfite and 50 to 100 parts of sodium hydroxide solution.
The cotton stalk lignin-based air entraining agent takes sodium sulfite as a reactant, the reaction is carried out under the conditions of high temperature, high pressure and alkalinity, the cotton stalk lignin-based air entraining agent is synthesized, the purity of the obtained cotton stalk lignin-based air entraining agent is about 90 percent, the purity of the cotton stalk lignin-based air entraining agent is high, the air entraining effect is good, and the air content of concrete can be improved to 5 to 10 percent under the optimal proportion when the cotton stalk lignin-based air entraining agent is applied to the concrete.
Example 2: the raw materials of the cotton stalk lignin-based air entraining agent comprise, by weight, 5 parts of cotton stalk lignin, 1 part or 10 parts of sodium sulfite and 50 parts or 100 parts of sodium hydroxide solution.
Example 3: as optimization of the embodiment, the cotton stalk lignin-based air entraining agent is obtained according to the following steps: firstly, mixing required amount of cotton stalk lignin, sodium sulfite and 50-100 parts of sodium hydroxide solution, and uniformly stirring to obtain a cotton stalk lignin mixed solution; secondly, heating the cotton stalk lignin mixed solution to 130-170 ℃ for reaction for 3-7 hours to obtain a reaction product; thirdly, cooling the reaction product to room temperature, neutralizing the reaction product with hydrochloric acid solution until the pH value of the reaction product is 7, carrying out suction filtration, purifying the obtained suction filtration liquid with anion-cation exchange resin, and neutralizing the purified liquid with sodium hydroxide solution until the pH value of the purified liquid is 7 to obtain the sodium lignosulfonate cotton stalk; fourthly, drying the cotton stalk lignin sodium sulfonate in vacuum at the temperature of 65-75 ℃ and under the pressure of-0.09 MPa to obtain the cotton stalk lignin-based air entraining agent.
The invention fully utilizes the agricultural waste cotton stalks to produce the economical and environment-friendly concrete air entraining agent by a simple and effective preparation method. Compared with the air entraining agent on the market, the air entraining agent has the advantages of simple preparation process, wide raw material source, lower cost and the like.
Example 4: as optimization of the above example, the concentration of the hydrochloric acid solution was 1 mol/L.
Example 5: as optimization of the above example, the concentration of the sodium hydroxide solution was 1 mol/L.
Example 6: the application of the cotton stalk lignin-based air entraining agent in concrete admixture.
The cotton stalk lignin-based air entraining agent is applied to concrete, can improve the air content of the concrete to 5-10% under the optimal proportion, can still keep the mechanical property of the concrete above 90% of that of the concrete without the air entraining agent, and has better effect than most of air entraining agents on the market.
Example 7: the cotton stalk lignin-based air entraining agent is obtained according to the following steps: firstly, mixing 5 parts of cotton stalk lignin, 50 parts of sodium hydroxide solution and 1 part of sodium sulfite, and uniformly stirring to obtain a cotton stalk lignin mixed solution; secondly, heating the cotton stalk lignin mixed solution to 130 ℃ for reaction for 3 hours to obtain a reaction product; thirdly, cooling the reaction product to room temperature, neutralizing the reaction product with 1mol/L hydrochloric acid solution until the pH value of the reaction product is 7, performing suction filtration, purifying the obtained suction filtration liquid with anion-cation exchange resin, and neutralizing the purified liquid with 1mol/L sodium hydroxide solution until the pH value of the purified liquid is 7 to obtain the sodium lignosulfonate cotton stalk; and fourthly, drying the cotton stalk lignin sodium sulfonate in vacuum at the temperature of 70 ℃ and under the pressure of-0.09 MPa to obtain the cotton stalk lignin-based air entraining agent. The purity of the cotton stalk lignin-based air entraining agent obtained by the embodiment is 90%, the gas content is 6%, and compared with the traditional lignosulfonate air entraining agent, the cotton stalk lignin-based air entraining agent has higher purity and higher gas content.
Example 8: the cotton stalk lignin-based air entraining agent is obtained according to the following steps: firstly, mixing and uniformly stirring 5 parts of cotton stalk lignin, 70 parts of sodium hydroxide solution and 5 parts of sodium sulfite to obtain a cotton stalk lignin mixed solution; secondly, heating the cotton stalk lignin mixed solution to 150 ℃ for reaction for 7 hours to obtain a reaction product; thirdly, cooling the reaction product to room temperature, neutralizing the reaction product with 1mol/L hydrochloric acid solution until the pH value of the reaction product is 7, performing suction filtration, purifying the obtained suction filtration liquid with anion-cation exchange resin, and neutralizing the purified liquid with 1mol/L sodium hydroxide solution until the pH value of the purified liquid is 7 to obtain the sodium lignosulfonate cotton stalk; and fourthly, drying the cotton stalk lignin sodium sulfonate in vacuum at the temperature of 70 ℃ and under the pressure of-0.09 MPa to obtain the cotton stalk lignin-based air entraining agent. The purity of the cotton stalk lignin-based air entraining agent obtained by the embodiment is 90.2%, the air content of the concrete is 8%, and compared with the traditional lignosulfonate air entraining agent, the cotton stalk lignin-based air entraining agent has higher purity and higher air content.
Example 9: the cotton stalk lignin-based air entraining agent is obtained according to the following steps: firstly, mixing and uniformly stirring 5 parts of cotton stalk lignin, 100 parts of sodium hydroxide solution and 10 parts of sodium sulfite to obtain a cotton stalk lignin mixed solution; secondly, heating the cotton stalk lignin mixed solution to 170 ℃ for reaction for 7 hours to obtain a reaction product; thirdly, cooling the reaction product to room temperature, neutralizing the reaction product with 1mol/L hydrochloric acid solution until the pH value of the reaction product is 7, performing suction filtration, purifying the obtained suction filtration liquid with anion-cation exchange resin, and neutralizing the purified liquid with 1mol/L sodium hydroxide solution until the pH value of the purified liquid is 7 to obtain the sodium lignosulfonate cotton stalk; and fourthly, drying the cotton stalk lignin sodium sulfonate in vacuum at the temperature of 70 ℃ and under the pressure of-0.09 MPa to obtain the cotton stalk lignin-based air entraining agent. The purity of the cotton stalk lignin-based air entraining agent obtained by the embodiment is 90.5%, the gas content is 10%, and compared with the traditional lignosulfonate air entraining agent, the cotton stalk lignin-based air entraining agent has higher purity and higher gas content.
In conclusion, the economic and environment-friendly concrete air entraining agent is produced by fully utilizing the agricultural waste cotton stalks, the raw material source is wide, the cost is low, the environment is protected, and the cotton stalk lignin-based air entraining agent is used as the concrete admixture, so that the air content of the concrete can be improved to 5-10%, and the mechanical property is kept unchanged.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (8)
1. The cotton stalk lignin-based air entraining agent is characterized by comprising 5 parts by weight of cotton stalk lignin, 1 to 10 parts by weight of sodium sulfite and 50 to 100 parts by weight of sodium hydroxide solution.
2. The cotton stalk lignin-based air entraining agent according to claim 1, which is characterized by being obtained by the following steps: firstly, mixing required amount of cotton stalk lignin, sodium sulfite and 50-100 parts of sodium hydroxide solution, and uniformly stirring to obtain a cotton stalk lignin mixed solution; secondly, heating the cotton stalk lignin mixed solution to 130-170 ℃ for reaction for 3-7 hours to obtain a reaction product; thirdly, cooling the reaction product to room temperature, neutralizing the reaction product with hydrochloric acid solution until the pH value of the reaction product is 7, carrying out suction filtration, purifying the obtained suction filtration liquid with anion-cation exchange resin, and neutralizing the purified liquid with sodium hydroxide solution until the pH value of the purified liquid is 7 to obtain the sodium lignosulfonate cotton stalk; fourthly, drying the cotton stalk lignin sodium sulfonate in vacuum at the temperature of 65-75 ℃ and under the pressure of-0.09 MPa to obtain the cotton stalk lignin-based air entraining agent.
3. The cotton stalk lignin-based air entraining agent according to claim 2, characterized in that the concentration of the hydrochloric acid solution is 1 mol/L.
4. The cotton stalk lignin-based air entraining agent according to claim 1, 2 or 3, characterized in that the concentration of the sodium hydroxide solution is 1 mol/L.
5. The preparation method of the cotton stalk lignin-based air entraining agent according to claim 1 is characterized by comprising the following steps: firstly, mixing required amount of cotton stalk lignin, sodium sulfite and 50-100 parts of sodium hydroxide solution, and uniformly stirring to obtain a cotton stalk lignin mixed solution; secondly, heating the cotton stalk lignin mixed solution to 130-170 ℃ for reaction for 3-7 hours to obtain a reaction product; thirdly, cooling the reaction product to room temperature, neutralizing the reaction product with hydrochloric acid solution until the pH value of the reaction product is 7, carrying out suction filtration, purifying the obtained suction filtration liquid with anion-cation exchange resin, and neutralizing the purified liquid with sodium hydroxide solution until the pH value of the purified liquid is 7 to obtain the sodium lignosulfonate cotton stalk; fourthly, drying the cotton stalk lignin sodium sulfonate in vacuum at the temperature of 65-75 ℃ and under the pressure of-0.09 MPa to obtain the cotton stalk lignin-based air entraining agent.
6. The method for preparing the cotton stalk lignin-based air entraining agent according to claim 5, wherein the concentration of the hydrochloric acid solution is 1 mol/L.
7. The method for preparing a cotton stalk lignin-based air entraining agent according to claim 5 or 6, characterized in that the concentration of the sodium hydroxide solution is 1 mol/L.
8. Use of the cotton stalk lignin-based air entraining agent according to claim 1, 2, 3 or 4 in concrete admixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911366961.3A CN111138109A (en) | 2019-12-26 | 2019-12-26 | Cotton stalk lignin-based air entraining agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911366961.3A CN111138109A (en) | 2019-12-26 | 2019-12-26 | Cotton stalk lignin-based air entraining agent and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111138109A true CN111138109A (en) | 2020-05-12 |
Family
ID=70520636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911366961.3A Pending CN111138109A (en) | 2019-12-26 | 2019-12-26 | Cotton stalk lignin-based air entraining agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111138109A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648979A (en) * | 2009-07-31 | 2010-02-17 | 福建科之杰新材料有限公司 | Preparation method for low air bleeding lignosulphonate high-efficiency water reducing agent |
| CN102585247A (en) * | 2012-01-12 | 2012-07-18 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing lignin sulfonate by utilizing residue from enzymatic hydrolysis of lignocellulose |
| CN102690423A (en) * | 2012-06-18 | 2012-09-26 | 河南省科学院化学研究所有限公司 | Method for producing sodium lignosulphonate by utilizing residues obtained by producing ethanol with crop straws as raw materials |
| CN103497342A (en) * | 2013-09-27 | 2014-01-08 | 山东龙力生物科技股份有限公司 | Method for producing enzymatic hydrolysis lignin sulfonate |
| CN105885058A (en) * | 2014-11-03 | 2016-08-24 | 吴迪 | Method utilizing crop straws to prepare sodium lignosulfonate |
| CN107474259A (en) * | 2016-06-08 | 2017-12-15 | 昌吉学院 | A kind of method that antioxidant sodium lignin sulfonate is prepared using cotton stalk |
| CN110078877A (en) * | 2019-04-26 | 2019-08-02 | 福州大学 | A kind of methods and applications preparing dispersing agent using lignin degradation products |
-
2019
- 2019-12-26 CN CN201911366961.3A patent/CN111138109A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648979A (en) * | 2009-07-31 | 2010-02-17 | 福建科之杰新材料有限公司 | Preparation method for low air bleeding lignosulphonate high-efficiency water reducing agent |
| CN102585247A (en) * | 2012-01-12 | 2012-07-18 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing lignin sulfonate by utilizing residue from enzymatic hydrolysis of lignocellulose |
| CN102690423A (en) * | 2012-06-18 | 2012-09-26 | 河南省科学院化学研究所有限公司 | Method for producing sodium lignosulphonate by utilizing residues obtained by producing ethanol with crop straws as raw materials |
| CN103497342A (en) * | 2013-09-27 | 2014-01-08 | 山东龙力生物科技股份有限公司 | Method for producing enzymatic hydrolysis lignin sulfonate |
| CN105885058A (en) * | 2014-11-03 | 2016-08-24 | 吴迪 | Method utilizing crop straws to prepare sodium lignosulfonate |
| CN107474259A (en) * | 2016-06-08 | 2017-12-15 | 昌吉学院 | A kind of method that antioxidant sodium lignin sulfonate is prepared using cotton stalk |
| CN110078877A (en) * | 2019-04-26 | 2019-08-02 | 福州大学 | A kind of methods and applications preparing dispersing agent using lignin degradation products |
Non-Patent Citations (1)
| Title |
|---|
| 阮承祥主编: "《混凝土外加剂及其工程应用》", 31 December 2008, 江西科学技术出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101161718A (en) | Biological degradation liquid film and preparation method | |
| US8987427B2 (en) | Highly efficient lignin-based water-reducing agent with high degree of sulfonation and high molecular weight, and preparation method thereof | |
| KR101728233B1 (en) | A method for manufacturing pellets for fuel using dis-used badges or logs after cultivation of mushrooms | |
| CN102417574B (en) | Biodegradable waterborne polyurethane sand fixing agent and preparation method thereof | |
| CN1884182A (en) | Civil engineering materials curing agent and preparation method thereof | |
| CN102212214B (en) | Biodegradable algae liquid plastic film and preparation method thereof | |
| CN102690423B (en) | Method for producing sodium lignosulphonate by utilizing residues obtained by producing ethanol with crop straws as raw materials | |
| CN101157531B (en) | Alkali lignin modified sulfamate high-effective water reducer and preparation method thereof | |
| CN101805144A (en) | Low-cost modified amino-sulfonic acid-based high-efficiency water reducer and preparation method thereof | |
| CN1966545A (en) | Enzymatic hydrolysis lignin epoxy resin material formula and its preparation method | |
| CN109777430A (en) | A kind of pH released microcapsule type macromolecule saline-alkali soil modifying agent and preparation method thereof | |
| KR20150023187A (en) | A method for manufacturing pellets for fuel using dis-used badges or logs after cultivation of mushrooms | |
| CN110129071B (en) | Lignin sand-fixing agent suitable for preventing and treating hillock erosion | |
| CN106348681A (en) | Soil solidifying agent and preparation method thereof | |
| CN112226233A (en) | Soil curing agent, cured soil and application thereof | |
| CN111138109A (en) | Cotton stalk lignin-based air entraining agent and preparation method and application thereof | |
| CN102442795B (en) | Method for preparing water reducing agent by using solid wastes of biomass acidic hydrolysis industry | |
| CN101735420B (en) | Preparation method and application method of biomass liquid agricultural membrane material | |
| CN109265058B (en) | Special additive for slope protection plant-growing concrete and preparation method thereof | |
| CN101913792B (en) | Method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer | |
| CN103305227A (en) | Black liquid state environment-friendly multifunctional mulching film | |
| CN101386502B (en) | Method for preparing porous desert greening brick | |
| CN114181709A (en) | Liquid soil curing agent for improving water resistance and preparation method thereof | |
| CN1408815A (en) | Sand fixing agent and its preparing method and use | |
| CN101386503B (en) | Method for preparing desert greening brick by inorganic gelation technology |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200512 |