CN101054271A - Preparation method of humic acids cement water reducing agent - Google Patents

Preparation method of humic acids cement water reducing agent Download PDF

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Publication number
CN101054271A
CN101054271A CNA2007100972732A CN200710097273A CN101054271A CN 101054271 A CN101054271 A CN 101054271A CN A2007100972732 A CNA2007100972732 A CN A2007100972732A CN 200710097273 A CN200710097273 A CN 200710097273A CN 101054271 A CN101054271 A CN 101054271A
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CN
China
Prior art keywords
reducing agent
humic acids
preparation
water reducing
cement water
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CNA2007100972732A
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Chinese (zh)
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CN100515976C (en
Inventor
王洁
赵跃山
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JINCHENG JUKUN BIOTECHNOLOGY CO Ltd
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JINCHENG JUKUN BIOTECHNOLOGY CO Ltd
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    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • 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
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/166—Macromolecular compounds comprising sulfonate or sulfate groups obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A cement water reducing agent has important functions to increase cement slurry fluidity, improve concrete strength and engineering quality. The invention relates to a preparing method of cement water reducer by using coal humic acid. The technology comprises: (1) Hydrolysis-oxidize pretreatment; (2) Extraction and sulphonation of humic acid; (3) solid-liquid separation; (4) atomized drying. The hydrolysis-oxidize, sulphonation and extraction and filtration are processed in one equipment, operation links are reduced greatly, equipment cost can be saved, work efficiency can be raised, product experimental performance is better than lignin sulfonate.

Description

A kind of preparation method of humic acids cement water reducing agent
1, technical field product of the present invention belongs to building materials chemical category, is specifically related to produce with coal humic acid (Humic Acid, code name HA) method of cement water reducing agent.
2, the background technology cement water reducing agent has vital role to increasing cement slurry degree of mobilization, raising concrete strength and construction quality.Water reducer commonly used is naphthalenesulfonate and sulfonated lignin etc., but often owing to the source is nervous, costing an arm and a leg has influenced use range.Replacing naphthalene system and Lignins product with other raw materials, is domestic and international development direction for many years.CN1066448 (1992) adopts acetone+formaldehyde+S-WAT to produce the sulfonated ketone aldehyde polycondensate, and its water reducer effect is better, but cost is higher, and processing condition are also harsh.CN1648099 (2005) adopts calcium lignin sulphonate (being called for short " wooden calcium "), Sulphanilic Acid, phenol, formaldehyde, alkali reaction to make multipolymer, and cost is also very high.CN1011218 (1987) carries out the semidrying reaction with peat+alkali lye+sulphonating agent to make peat HA water reducer, but owing in the product a large amount of water soluble saccharide are arranged, causes the grout foaming, has influenced result of use.
3, the peat of brown coal, weathered coal or the low level high de-agglomeration degree of summary of the invention the present invention HA content 〉=40%, make cement water reducing agent through hydrolysis-oxidation, sulfonation or sulfomethylation, raw material sources are extensive, with low cost, and its performance surpasses general wooden calcium water reducer.
Hydrolysis-oxidation in the technology of the present invention, sulfonation, extraction, filtration are carried out in same device (withstand voltage, logical steam heating is equipped with 500 ~ 800 order filter clothes), have greatly reduced operation link, have saved facility investment, have improved work efficiency.
Technological process of the present invention is as follows:
1, hydrolysis-oxidation pre-treatment: this step purpose is to improve the HA activity, decomposes and removes deleterious carbohydrate.To pulverize 60 purpose feed coals, oxygenant, water and put into the withstand voltage reaction-dynamic filtration integrated apparatus of band heating jacket by 1: 0.05～0.1: 6～8 (by the dry weight), its oxygenant is KMnO 4, HNO 3, H 2O 2, or NaClO.With NaOH or H 2SO 4Slurry is transferred to pH=4～5, reacts 1～3h down at 80～100 ℃.Open Filter valve, (0.2～0.4MPa) filters, and uses the suitable quantity of water washing leaching cake under agitation to use pressurized with compressed air.Filtrate and washing lotion recycle after desalination and biochemical treatment.Filter cake is dammed in device.
2, sulfonation or sulfomethylation: in feed coal (having become filter cake): sulphonating agent (or azochlorosulfonate methyl agent): alkali: the ratio of water=1: 0.1～0.4: 0.1～0.2: 6～8 adds reaction-strainer, airtightly afterwards reacts 1 ~ 3h under 90～150 ℃, normal pressure～0.6MPa.Used sulphonating agent is Na 2SO 3, NaHSO 3, or Na 2S 2O 5Used sulfomethylation reagent is the product with molal weight formaldehyde complex reactions such as above-mentioned sulphonating agents; Used alkali is NaOH, KOH or Na 2CO 3
3, filter: open Filter valve and scraper plate agitator, under the air pressure of 0.2～0.5MPa, filter, use the suitable quantity of water washing leaching cake.With filtrate and washing lotion merge A liquid.
4, drying: with the dry A liquid of spray-drier, hot-air inlets temperature≤300 ℃, temperature out≤80 ℃, time of drying 2 ~ 5s, powdery water reducer product.
4, embodiment
Example 1
In 1M3 reaction-filtering integral device, add entry 500L successively, brown coal powder (60 orders, HA d=54.3%) 70kg, 30%H 2O 27L, 92%H 2SO 41.2L, start stirring, with steam heating to 90 ℃, reaction 2h filters with air pressurized (0.2MPa), with 200L water washing filter cake.In device, add NaHSO 320kg, NaOH 8kg, water 400L airtightly heats up down, reacts 2h under 120 ℃, 0.2MPa.Open Filter valve and scraper plate agitator, pressurization (0.3MPa) is filtered, with 300L water washing filter cake.Merging filtrate and washing lotion to the cat head drying of spraying, get powder-like product 59.4kg with its pump, and yield is equivalent to 84.9% of feed coal.
Example 2:
Add sulfomethylation reagent 41kg (NaHSO in the filter cake behind oxydrolysis 320kg+37% HCHO 21kg), all the other conditions get product 60.2kg with embodiment 1.
Embodiment 3:
Press the method for GB13590-1992, in homogenizer, put into slag cement 300g No. 425, various cement water reducing agent 1g, and compare test [comprise not adding water reducer, add wooden calcium (Mudanjiang product)], high-speed stirring 3min pours out cement, measures clean slurry degree of mobilization.Method by GB7897.7-1987 is measured the test block ultimate compression strength of mixing under the 0.3% water reducer situation.Measurement result sees Table.
Water reducer of the present invention and calcium lignin sulphonate property comparison test-results
Sample Clean slurry degree of mobilization Ultimate compression strength
mm Δ％ 28 days (R 28)kg Water-reducing rate, %
Blank (not adding water reducer) calcium lignin sulphonate sulfonation HA (embodiment 1) sulfomethylation HA (embodiment 2) 98 141 169 175 --- 43.9 72.4 78.6 324.5 409.2 423.7 455.2 17.0 20.5 22.3
From the table data as seen, the performance of product of the present invention obviously is better than wooden calcium, sulfomethylated HA product is better than sulfonation HA.

Claims (6)

1, a kind of preparation method of humic acids cement water reducing agent is characterized in that used raw material is weathered coal, brown coal or the low level high de-agglomeration degree peat of humic acids content 〉=40%.
2, the preparation method of humic acids cement water reducing agent as claimed in claim 1 is characterized in that hydrolysis-oxidation, sulfonation, extraction, filtration carry out in same device, 500-800 order filter cloth is housed in the device.
3, the preparation method of humic acids cement water reducing agent as claimed in claim 1 is characterized in that being undertaken by following technological process:
(1) hydrolysis-oxidation pre-treatment: pulverized 60 purpose feed coals, oxygenant, water by dry weight, and put into reaction-filtration unit in 1: 0.05～0.1: 6～8 ratio, ℃ following reaction is 1～3 hour in pH=4～5,80～100.Air pressurized 0.2～0.4MPa filters, and uses the suitable quantity of water washing leaching cake;
(2) sulfonation or sulfomethylation: in feed coal: sulphonating agent or azochlorosulfonate methyl agent: alkali: the ratio of water=1: 0.1～0.4: 0.1～0.2: 6～8 adds reaction-strainer, airtightly afterwards reacts 1～3 hour under 90～150 ℃, normal pressure～0.6MPa;
(3) filter: under the air pressure of 0.2～0.5MPa, filter, use the suitable quantity of water washing leaching cake;
(4) drying: filtrate with spray-drier, in inlet temperature≤300 ℃, temperature out≤80 are ℃ dry down, powdery water reducer product.
4, the preparation method of humic acids cement water reducing agent as claimed in claim 3 is characterized in that used oxygenant is KMnO 4, HNO 3, H 2O 2, or NaClO.
5, the preparation method of humic acids cement water reducing agent as claimed in claim 3 is characterized in that used sulphonating agent is Na 2SO 3, NaHSO 3, or Na 2S 2O 5Used sulfomethylation reagent is the product with molal weight complex reactions such as above-mentioned sulphonating agents; Used alkali is NaOH, KOH or Na 2CO 3
6, the preparation method of humic acids cement water reducing agent as claimed in claim 3 is characterized in that with the dry the finished product of spray-drier.
CNB2007100972732A 2007-04-29 2007-04-29 Preparation method of humic acids cement water reducing agent Expired - Fee Related CN100515976C (en)

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CN100515976C CN100515976C (en) 2009-07-22

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554191A (en) * 2013-11-07 2014-02-05 太原师范学院 Preparation method of humic acid biostimulant and prepared biostimulant
CN104386942A (en) * 2014-10-28 2015-03-04 淮南天泉建材有限公司 Fly ash concrete treating agent and preparation methods thereof
CN106045688A (en) * 2016-06-01 2016-10-26 卞佳林 Preparation method of humic acid compound fertilizer
CN106750076A (en) * 2017-01-24 2017-05-31 福州大学 A kind of preparation method and applications of cement water reducing agent
CN109305817A (en) * 2018-10-29 2019-02-05 江西省欧陶科技有限公司 A kind of ceramics degumming agent and preparation method thereof
CN111116260A (en) * 2020-01-03 2020-05-08 浙江丰瑜生态科技股份有限公司 Water-soluble fertilizer containing humic acid and preparation method thereof
CN111333358A (en) * 2020-05-08 2020-06-26 中建西部建设西南有限公司 Concrete antifreezing agent and preparation method and application thereof
CN111560121A (en) * 2020-04-03 2020-08-21 安徽工业大学 Preparation method of modified lignite humic acid water reducer
CN113336468A (en) * 2021-06-29 2021-09-03 上海臻衍生物科技有限公司 Efficient composite humic acid drilling water reducer and application
CN113480360A (en) * 2021-07-27 2021-10-08 海南金雨丰生物工程有限公司 Humic acid fertilizer and preparation method thereof

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554191A (en) * 2013-11-07 2014-02-05 太原师范学院 Preparation method of humic acid biostimulant and prepared biostimulant
CN103554191B (en) * 2013-11-07 2016-04-13 太原师范学院 The biostimulant of a kind of humic acid biological yield stimulant preparation method and preparation
CN104386942A (en) * 2014-10-28 2015-03-04 淮南天泉建材有限公司 Fly ash concrete treating agent and preparation methods thereof
CN106045688A (en) * 2016-06-01 2016-10-26 卞佳林 Preparation method of humic acid compound fertilizer
CN106750076A (en) * 2017-01-24 2017-05-31 福州大学 A kind of preparation method and applications of cement water reducing agent
CN109305817A (en) * 2018-10-29 2019-02-05 江西省欧陶科技有限公司 A kind of ceramics degumming agent and preparation method thereof
CN111116260A (en) * 2020-01-03 2020-05-08 浙江丰瑜生态科技股份有限公司 Water-soluble fertilizer containing humic acid and preparation method thereof
CN111116260B (en) * 2020-01-03 2021-09-10 浙江丰瑜生态科技股份有限公司 Water-soluble fertilizer containing humic acid and preparation method thereof
CN111560121A (en) * 2020-04-03 2020-08-21 安徽工业大学 Preparation method of modified lignite humic acid water reducer
CN111560121B (en) * 2020-04-03 2022-03-04 安徽工业大学 Preparation method of modified lignite humic acid water reducer
CN111333358A (en) * 2020-05-08 2020-06-26 中建西部建设西南有限公司 Concrete antifreezing agent and preparation method and application thereof
CN113336468A (en) * 2021-06-29 2021-09-03 上海臻衍生物科技有限公司 Efficient composite humic acid drilling water reducer and application
CN113480360A (en) * 2021-07-27 2021-10-08 海南金雨丰生物工程有限公司 Humic acid fertilizer and preparation method thereof

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