CN1240199A - High-efficient wet-process cement raw slurry thinning agent - Google Patents
High-efficient wet-process cement raw slurry thinning agent Download PDFInfo
- Publication number
- CN1240199A CN1240199A CN 98114593 CN98114593A CN1240199A CN 1240199 A CN1240199 A CN 1240199A CN 98114593 CN98114593 CN 98114593 CN 98114593 A CN98114593 A CN 98114593A CN 1240199 A CN1240199 A CN 1240199A
- Authority
- CN
- China
- Prior art keywords
- wet
- thinning agent
- raw slurry
- cement raw
- process cement
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000004568 cement Substances 0.000 title claims abstract description 24
- 239000002002 slurry Substances 0.000 title claims abstract description 17
- 239000012749 thinning agent Substances 0.000 title claims abstract description 13
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229920005610 lignin Polymers 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000010902 straw Substances 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003467 diminishing effect Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- 241001274216 Naso Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019357 lignosulphonate Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
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
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Paper (AREA)
Abstract
The present invention relates to a thinning agent for wet-process cement raw slurry, belonging to an additive for wet-process cement slurry. It is characterized by that the sulfate (or alkali) lignin extracted from "black liquor" of paper-making pulp using straw as raw material is modified by sulfonation, and its solubility and activity are greatly raised, so that it can be directly used as thinning agent for raw slurry in the course of cement production by wet method or semi-dry method. As compared with existent technology, addition of said additive can reduce water consumption by above 30%, and can eliminate the contamination of paper-making black liquor to environment, and can have the energy consumption of wet cement production reduced to obtain obvious energy-saving effect.
Description
The invention belongs to the additive of charge pulp in the wet-process cement production, be a kind of high-efficient wet-process cement raw slurry thinning agent, be about to the thinner that is used as the wet-process cement charge pulp " black liquor " of raw pulp papermaking with the sulphur-modified back of vitriol (or alkali) xylogen of acid system extractions from being with the grass.
Pulping and paper-making mainly contains two class methods by the raw material difference:
＜one 〉, be the sulfitation process craft route of raw material with timber, but the by-product sulfonated lignin claim sulfonated lignin again, are industrial broad-spectrum tensio-active agents, as dye dispersant, concrete alkali aqua etc.Generally believe in the sulfonated lignin macromolecular structure and on the carbon atom of benzene ring side chain, be connected with-SO
3 -Group, its good water solubility is not influenced by solution PH.＜two 〉, with the herbaceous plant be the sulphate process technologies such as (or alkaline process) of raw material, its raw material has wheat straw, Herba Poae Sphondylodis, reed, bagasse etc., in the black liquor that from this method production process, produces, means such as available acid system are extracted the rugose wood element and (are wherein also included polysaccharide etc., composition is very complicated), be called vitriol (or alkali) xylogen, it is only soluble in the basic solution of PH＞7.Because vitriol lignin dissolution degree is low, poor activity so industrial use is few, thereby has also restricted the improvement of papermaking " black liquor ", becomes well-known public hazards.
Low at vitriol lignin dissolution degree in the prior art; poor activity and restricted in industrial use; cause papermaking " black liquor " to be difficult to administer and become the problem of public hazards; the objective of the invention is to: a kind of high-efficient wet-process cement raw slurry thinning agent is provided; be about to lower vitriol (or alkali) the xylogen sulfonation modification of solubleness; make it in the xylogen macromole, introduce sulfonic acid group; improve its solubleness and surfactivity; again with the thinner of the vitriol xylogen behind the sulfonation modifying as wet method or semidrying cement raw slurry; it has good water-reducing effect and grinding aid effect; it is effective energy-saving material during wet-process cement is produced; and black liquid is turned waste into wealth; promote to administer protection environment and energy-saving and cost-reducing meaning.
The present invention realizes like this: adopt vitriol (or alkali) xylogen sulfonation modification or sulphur-modified based on the complexification thing of this type of modifier or natural organic high-molecular compound and the main material that is made of natural high moleculer eompound, or its compound, all can be used as the thinner of wet method, semidrying cement raw slurry.The sulfonation modifying of vitriol xylogen has two kinds of non-pressure process and pressurizations, shows through infrared analysis, adopts the xylogen of non-pressure process modification ,-SO
3 -Group mainly is to be connected on the phenyl ring; And pressurization is during sulfonation, since the temperature of reaction height ,-SO
3 -Group mainly is connected on the side chain of phenyl ring.
During the normal pressure sulfonation, temperature of reaction is low, between 50～100 ℃, is activator with formaldehyde, makes vitriol xylogen and NaSO
3Reaction promptly got normal pressure sulfonation modifying xylogen more than 1 hour; During pressurization, do not use activator, can under the pressure about 0.65MPa, under the temperature condition about 170 ℃, make vitriol xylogen and NaSO
3Direct reaction got final product in 3 hours in reactor, and the sulfonation modifying xylogen obtains pressurizeing.The sulfonation modifying lignin liquor that above dual mode obtains need not be done other processing and just can directly be used as wet-process cement raw slurry thinning agent.
Variation by GB B8077-87 " Methods for testing uniformity of concrete admixture " test charge pulp degree of mobilization before and after the above-mentioned thinner of interpolation, according to (degree of mobilization-amount of water) shown in Figure 1 curve, reading charge pulp, to add behind the thinner its degree of mobilization pairing be theoretical amount of water, the difference of the actual water content of this amount and charge pulp is the diminishing amount, measures water-reducing rate thus.Slip water content as standard of comparison is high more, and then corresponding diminishing amount increases, otherwise then reduces, and water-reducing rate is relevant with the slip initial moisture content.
Experiment showed, natural organic-compound, the material that the natural organic high-molecular compound constitutes, sulphur-modified after, or after sulfonation the compound of modification again, wet method, semidrying cement raw slurry are all had water-reduction, can be as their thinner.
Compared with the prior art, technology of the present invention is simple, gained sulfonation modifying xylogen, need not to do other processing, just can directly be used as wet method, semidrying cement raw slurry thinning agent, can reduce more than 38% of consumption of water in the cement production process, both can eliminate the pollution of black liquid environment, turn waste into wealth, can make wet-process cement production reach considerable energy saving consumption reduction effect again.
Description of drawings: Fig. 1 slip degree of mobilization-amount of water curve of making a living
Embodiment one,
Get thick lignin 7.16g of commercial sulfuric acid salt and anhydrous Na SO
310.4g, be dissolved in the 50mlNaOH solution, add 37% formalin 2.4ml again, in 60 ℃ of reactions 2 hours, the gained reaction solution was normal pressure sulfonation modifying xylogen, can be used as cement raw slurry thinning agent.
Water 105ml, raw material dry powder 300g and 2.5g, xylogen sample behind the above-mentioned sulfonation modifying is after cement expects to stir 3 minutes in the stirrer only, survey its degree of mobilization, the gained degree of mobilization is equivalent to contain the degree of mobilization of the slip of pure water 171ml, so the diminishing amount is 66g, is 38.6% (to water) to raw material powder water-reducing rate then.
Embodiment two,
Get vitriol xylogen 28.60g, NaSO
341.6g NaOH 4g and 800ml deionized water, after the stirring and dissolving, airtight heat temperature raising was in 170 ℃ of reactions 4 hours in autoclave pressure, and the sulfonation modifying xylogen must pressurize.
Survey its degree of mobilization with embodiment one, 100g raw material powder diminishing amount is reached 21g water-reducing rate 37.5% (to water).
Claims (2)
1, a kind of high-efficient wet-process cement raw slurry thinning agent is characterized in that: with sulfonation modifying vitriol xylogen or alkali lignin, directly as wet-process cement raw slurry thinning agent, its water-reducing rate can reach more than 30%.
2, according to the described high-efficient wet-process cement raw slurry thinning agent of claim 1, its technical characterictic is: also can directly be used as wet-process cement raw slurry thinning agent after other natural high moleculer eompound is sulphur-modified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114593A CN1115310C (en) | 1998-06-20 | 1998-06-20 | High-efficient wet-process cement raw slurry thinning agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114593A CN1115310C (en) | 1998-06-20 | 1998-06-20 | High-efficient wet-process cement raw slurry thinning agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1240199A true CN1240199A (en) | 2000-01-05 |
| CN1115310C CN1115310C (en) | 2003-07-23 |
Family
ID=5224233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114593A Expired - Fee Related CN1115310C (en) | 1998-06-20 | 1998-06-20 | High-efficient wet-process cement raw slurry thinning agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1115310C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101370745B (en) * | 2005-11-14 | 2012-04-25 | 新日本石油株式会社 | Binding material comprising modified sulphur and method for preparing a material comprising modified sulphur |
| CN105713164A (en) * | 2016-01-27 | 2016-06-29 | 华北水利水电大学 | Aliphatic water reducer prepared from straw and preparation method thereof |
| CN110963723A (en) * | 2018-09-30 | 2020-04-07 | 台山市翔隆纸业有限公司 | Method for producing cement clinker by using papermaking wastewater |
-
1998
- 1998-06-20 CN CN98114593A patent/CN1115310C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101370745B (en) * | 2005-11-14 | 2012-04-25 | 新日本石油株式会社 | Binding material comprising modified sulphur and method for preparing a material comprising modified sulphur |
| CN105713164A (en) * | 2016-01-27 | 2016-06-29 | 华北水利水电大学 | Aliphatic water reducer prepared from straw and preparation method thereof |
| CN110963723A (en) * | 2018-09-30 | 2020-04-07 | 台山市翔隆纸业有限公司 | Method for producing cement clinker by using papermaking wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1115310C (en) | 2003-07-23 |
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