CN103938478A - Cement grinding aid and method for fabricating cement grinding aid by using papermaking waste liquor - Google Patents
Cement grinding aid and method for fabricating cement grinding aid by using papermaking waste liquor Download PDFInfo
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- CN103938478A CN103938478A CN201410152320.9A CN201410152320A CN103938478A CN 103938478 A CN103938478 A CN 103938478A CN 201410152320 A CN201410152320 A CN 201410152320A CN 103938478 A CN103938478 A CN 103938478A
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Abstract
The invention discloses a cement grinding aid. In the cement grinding aid, lignosulfonate accounts for 3-8% weight of the cement grinding aid. The invention also discloses a method for fabricating a cement grinding aid by using papermaking waste liquor. The papermaking waste liquor comprises basic black liquor and basic red liquor. The method comprises the following steps: 1) participating the papermaking waste liquor to remove mud; 2) entering the liquid into an anaerobic fermentation device to carry out fermentation treatment; 3) filtering the liquid after fermentation treatment to obtain a solid lignin salt or filtrate; 4) baking the lignin salt to form the product; 5) heating the filtrate to 60-65 DEG C, injecting into a product agitator bath, and agitating to obtain the product, wherein the gas, solid and liquid generated from the papermaking waste liquor by biochemical fermentation treatment are fully utilized and finished in a sealed technological condition, not only is a machining operation facilitated, but also secondary pollution to the environment is not generated.
Description
Technical field
The present invention relates to cement and manufacture field, particularly a kind of cement grinding aid, also relates to a kind of method of utilizing papermaking wastewater to make cement grinding aid.
Background technology
The waste liquid of pulping and digesting workshop section discharge accounts for the more than 80% of papermaking wastewater pollution sources, administer difficulty large, investing many technical requirements height is the key of restriction paper-making industry development, the slurrying dope of paper mill cooking section discharge contains a large amount of lignosulfonates, and lignosulfonates are the important source material of producing high-efficiency concrete grinding aid.The lignosulfonates that facilitate ingredient stability in order to obtain batching, we have researched and developed with processing extractive technique in the alkaline black liquor of papermaking and acid red liquid, obtain promising result.
The present invention crosses precipitation cooking section waste liquid pool back warp to go the waste liquid after mud to filter, analyze the content of effective ingredient, process produced gas by biochemical fermentation and can be used as industrial fuel, the solid of separating and filtering is as industrial chemicals, and the lignosulfonates that contain in liquid after separating are as producing cement grinding aid raw material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of cement grinding aid, contain lignosulfonates, a kind of method of utilizing papermaking wastewater to make cement grinding aid is also provided, in alkaline black liquor by papermaking and acid red liquid, lignosulfonates are extracted in processing, to solve the above-mentioned multinomial defect causing in prior art.
For achieving the above object, the invention provides following technical scheme: a kind of cement grinding aid, is characterized in that: the shared weight ratio 3-8% of lignosulfonates in described cement grinding aid.
Utilize the method that in papermaking wastewater, acid red liquid is made cement grinding aid, it is characterized in that: comprise the steps:
1) papermaking wastewater precipitation is removed mud;
2) liquid enters and in anaerobic fermentation device, carries out fermentation process;
3) liquid after fermentation process is carried out to filtration treatment, obtain lignin salt and the filtrate of solid;
4) lignin salt is finished product after drying;
5) filtrate is heated to after 60--65 DEG C, injects finished product agitator tank (bath), stirs and makes finished product.
Preferably, described step 2) in, the time of anaerobic fermentation processing is 10--20 days; The temperature of anaerobic fermentation is 35--45 DEG C.
Preferably, described anaerobic fermentation device is connected with boiler, produces CH in anaerobic fermentation process
4, by CH
4lead to boiler boiler is heated, the hot water of boiler heating leads to anaerobic fermentation device; The temperature of hot water is controlled at 40--50 DEG C.
Preferably, in described step 5), be finished product after adding in proportion urea, triethanolamine, ethylene glycol, acetic acid fully to stir according to the content of lignosulfonates in filtrate.
Utilize papermaking wastewater neutral and alkali black liquor to make a method for cement grinding aid described in claim 1, it is characterized in that: comprise the steps:
1) papermaking wastewater precipitation is removed mud;
2) deliver in sulphonator, carry out sulfonation processing;
3) liquid enters and in anaerobic fermentation device, carries out fermentation process;
4) liquid after fermentation process is carried out to filtration treatment, obtain lignin salt and the filtrate of solid;
5) lignin salt is finished product after drying;
6) filtrate is heated to after 60--65 DEG C, injects finished product agitator tank (bath), stirs and makes finished product.
Preferably, described step 2) in, in sulphonator, pass into SO
2, or add H
2sO
3carry out sulfonation processing.
Preferably, in described step 3), the time of anaerobic fermentation processing is 10--20 days; The temperature of anaerobic fermentation is 35--45 DEG C.
Preferably, described anaerobic fermentation device is connected with boiler, produces CH in anaerobic fermentation process
4, by CH
4lead to boiler boiler is heated, the hot water of boiler heating leads to anaerobic fermentation device; The temperature of hot water is controlled at 40--50 DEG C.
Preferably, in described step 6), be finished product after adding in proportion urea, triethanolamine, ethylene glycol, acetic acid fully to stir according to the content of lignosulfonates in filtrate.
Adopt the beneficial effect of above technical scheme to be: the present invention crosses precipitation cooking section waste liquid pool back warp to go the waste liquid after mud to filter, analyze the content of effective ingredient, process produced gas by biochemical fermentation and can be used as industrial fuel, the solid of separating and filtering is as industrial chemicals, and the lignosulfonates that contain in liquid after separating can be used as production cement grinding aid; Anaerobic fermentation device is connected with boiler, produces CH in anaerobic fermentation process
4, by CH
4leading to boiler heats boiler, the hot water of boiler heating leads to anaerobic fermentation device, the pulping waste liquor discharging by paper mill evaporation section is by biochemical fermentation processing, the gas, solid and the liquid that generate are all fully used, and be to complete under the process conditions of sealing, not only facilitate process operation, can not cause the secondary pollution to environment simultaneously.
Brief description of the drawings
Fig. 1 is a kind of process chart that utilizes papermaking wastewater to make cement grinding aid of the present invention.
Detailed description of the invention
A kind of cement grinding aid, the shared weight ratio 3-8% of lignosulfonates in cement grinding aid, produces to carry and produces serial cement grinding aid, and the weight ratio 3--5% that lignosulfonates are shared, produces enhanced type grinding aids, the weight ratio 4--8% that lignosulfonates are shared.
Describe a kind of preferred embodiment of utilizing papermaking wastewater to make cement grinding aid of the present invention in detail below in conjunction with accompanying drawing.
Fig. 1 shows the specific embodiment of the present invention: a kind of method of utilizing acid red liquid making cement grinding aid in papermaking wastewater, comprises the steps:
1) papermaking wastewater precipitation is removed mud;
2) liquid enters and in anaerobic fermentation device, carries out fermentation process;
3) liquid after fermentation process is carried out to filtration treatment, obtain lignin salt and the filtrate of solid;
4) lignin salt is finished product after drying;
5) filtrate is heated to after 60--65 DEG C, injects finished product agitator tank (bath), stirs and makes finished product.
Step 2) in, the time of anaerobic fermentation processing is 10--20 days; The temperature of anaerobic fermentation is 35--45 DEG C.
Anaerobic fermentation device is connected with boiler, produces CH in anaerobic fermentation process
4, by CH
4lead to boiler boiler is heated, the hot water of boiler heating leads to anaerobic fermentation device; The temperature of hot water is controlled at 40--50 DEG C.
In step 5), be finished product after adding in proportion urea, triethanolamine, ethylene glycol, acetic acid fully to stir according to the content of lignosulfonates in filtrate.
Utilize papermaking wastewater neutral and alkali black liquor to make a method for cement grinding aid, it is characterized in that: comprise the steps:
1) papermaking wastewater precipitation is removed mud;
2) deliver in sulphonator, carry out sulfonation processing;
3) liquid enters and in anaerobic fermentation device, carries out fermentation process;
4) liquid after fermentation process is carried out to filtration treatment, obtain lignin salt and the filtrate of solid;
5) lignin salt is finished product after drying;
6) filtrate is heated to after 60--65 DEG C, injects finished product agitator tank (bath), stirs and makes finished product.
Step 2) in, in sulphonator, pass into SO
2, or add H
2sO
3carry out sulfonation processing.
In step 3), the time of anaerobic fermentation processing is 10--20 days; The temperature of anaerobic fermentation is 35--45 DEG C.
Anaerobic fermentation device is connected with boiler, produces CH in anaerobic fermentation process
4, by CH
4lead to boiler boiler is heated, the hot water of boiler heating leads to anaerobic fermentation device; The temperature of hot water is controlled at 40--50 DEG C.
In step 6), be finished product after adding in proportion urea, triethanolamine, ethylene glycol, acetic acid fully to stir according to the content of lignosulfonates in filtrate.
In the black liquor of alkaline pulp-making cooking section discharge, the content of lignosulfonates is 12--14%, delivers to and in sulphonator, pass into SO after precipitation is removed mud in the waste liquid settling tank in paper mill
2, or add H
2sO
3carry out sulfonation processing, make pH value drop to 5 left and right, the liquid of sulfonation is carried out in anaerobic fermentation device to fermentation process, utilize the organic compound of anaerobism saccharomycete in the condition decline liquid waste solution of anaerobic, make macromolecular organic compound Degradation and Transformation become micromolecular stable compound, and have a large amount of organic acids to produce.Release energy with the form of methane simultaneously.Anaerobism saccharomycete is breeding rapidly in the fermentor of 40 DEG C, and lignosulfonates are had to stronger adsorption capacity and flocculation.In producing a large amount of flocculates, produce a lot of fuel gas CH
4,according to producing the requirement of cement grinding aid to lignin sulfonic acid salt content in liquid, through the fermentation process of 10--20 days, the lignosulfonates filtering drying that a part is formed to solid was as industrial chemicals, and the liquid after filtration is for the production of cement grinding aid.
The time of anaerobic fermentation is that the shared ratio of lignosulfonates is determined during according to production different cultivars cement grinding aid.Production is carried and is produced serial cement grinding aid, and the weight ratio 3--5% that lignosulfonates are shared, produces enhanced type grinding aids, the weight ratio 4--8% that lignosulfonates are shared.If the shared ratio of lignosulfonates is large, fermentation time can be shorter, in liquid, the content of lignosulfonates is just large, general control just can meet the requirement of producing cement grinding aid at 10--20 days, if lignosulfonates containing quantity not sufficient in liquid, the solid lignin sulfonate filtering out can be added to adjusting, under the hydrotropy of triethanolamine, can again be dissolved in solution.
The calcium lignosulfonate pH value that contains 11--12% in the maroon waste liquid of acid polishing cooking section discharge is generally below 5, precipitation goes the liquid after mud not need sulfonation and fall pH value processing, can directly enter fermentor and carry out anaerobic fermentation processing, the process conditions of processing are undertaken by anaerobic fermentation way after treatment.
Coil pipe in fermentor can pass into hot water or circulating water control waste liquid temperature 40 DEG C of left and right.At this temperature, anaerobism saccharomycete breeding is very fast, in forming a large amount of flocculation sediments, discharges a lot of CH4 gas, and gas carries out delivering to after the explosion precaution of aqueous vapor isolation the furnace fuel as a supplement of boiler by water seal.The lignin salt of precipitation collects after filter filters, and drying had been both finished product, and the filtrate after filtration is delivered to and produced cement grinding aid operation.
In analysis filtrate, being heated to 60--65 DEG C after the content of lignosulfonates injects in finished product agitator tank (bath), after adding in proportion urea, triethanolamine, ethylene glycol, acetic acid fully to stir according to the content of lignosulfonates, be finished product, after analysis, pack simultaneously.
The solid lignin sulfonate that fermentation generates can be used for adjusting cement grinding aid content ratio.Lignosulfonates can activate the activity of cement mixture, promote hydrated cementitious condensation process, improve the early strength of cement; Lignosulfonates are also concrete mixing plant shrink additives, can also be used in process hides printing and dyeing etc. industrial.Lignosulfonates have asymmetric molecular structure, in the different trends in the surface of molecule, show certain energy, can balance cement grinding mill in Electrostatic Absorption on fine particle, eliminate the bed course of liner plate and abrasive body, therefore can improve mill output.Because granule is not attracted on bulky grain, improve grinding efficiency and also can not cause secondary to cross grinding.
It is to use the cement of different composite materials and production different cultivars to determine the consumption match ratio of lignosulfonates, triethanolamine, urea, ethylene glycol, acetic acid according to manufacture of cement that waste liquid after filtration is produced cement grinding aid.Carry product type grinding aid and be added to the power consumption reduction 3--8 degree that can make the unit-hour output raising 10--30% of cement grinding mill produce cement per ton in cement grinding mill; The grinding aid of enhancement mode can make to produce 3 days and the strength increase 6--8Mpa of 28 days of cement, can make the grog of producing cement reduce 5--7% in the situation that unit-hour output is constant, and composite material increases 5--7% and do not affect the original quality of cement.Remove with the production cost reduction 8--12 unit that makes cement per ton after grinding aid cost, the consumption of carrying product type and enhanced type grinding aids is the 0.02--0.03% that produces cement.
Reach 5 left and right because the saccharomycetic effect of anaerobism has produced the pH value that a part of organic acid makes waste liquid in anaerobic fermentation device, add urea, triethanolamine, ethylene glycol after pH value be raised to 7--9.Can make pH value drop to the needs that just can adapt to produce low alkali cement below 7 by adjusting the consumption of acetic acid, the domestic and international grinding aid of selling be in the market all generally that alkalescence does not possess such condition.
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (10)
1. a cement grinding aid, is characterized in that: the shared weight ratio 3-8% of lignosulfonates in described cement grinding aid.
2. utilize acid red liquid in papermaking wastewater to make a method for cement grinding aid described in claim 1, it is characterized in that: comprise the steps:
1) papermaking wastewater precipitation is removed mud;
2) liquid enters and in anaerobic fermentation device, carries out fermentation process;
3) liquid after fermentation process is carried out to filtration treatment, obtain lignin salt and the filtrate of solid;
4) lignin salt is finished product after drying;
5) filtrate is heated to after 60--65 DEG C, injects finished product agitator tank (bath), stirs and makes finished product.
3. the method for utilizing acid red liquid making cement grinding aid in papermaking wastewater according to claim 2, is characterized in that: described step 2) in, the time of anaerobic fermentation processing is 10--20 days; The temperature of anaerobic fermentation is 35--45 DEG C.
4. according to the method that in papermaking wastewater, acid red liquid is made cement grinding aid of utilizing described in claim 2 or 3, it is characterized in that: described anaerobic fermentation device is connected with boiler, produces CH in anaerobic fermentation process
4, by CH
4lead to boiler boiler is heated, the hot water of boiler heating leads to anaerobic fermentation device; The temperature of hot water is controlled at 40--50 DEG C.
5. the method for utilizing acid red liquid making cement grinding aid in papermaking wastewater according to claim 2, it is characterized in that: in described step 5), be finished product after adding in proportion urea, triethanolamine, ethylene glycol, acetic acid fully to stir according to the content of lignosulfonates in filtrate.
6. utilize papermaking wastewater neutral and alkali black liquor to make a method for cement grinding aid described in claim 1, it is characterized in that: comprise the steps:
Papermaking wastewater precipitation is removed mud;
Deliver in sulphonator, carry out sulfonation processing;
3) liquid enters and in anaerobic fermentation device, carries out fermentation process;
4) liquid after fermentation process is carried out to filtration treatment, obtain lignin salt and the filtrate of solid;
5) lignin salt is finished product after drying;
6) filtrate is heated to after 60--65 DEG C, injects finished product agitator tank (bath), stirs and makes finished product.
7. the method for utilizing papermaking wastewater neutral and alkali black liquor to make cement grinding aid according to claim 6, is characterized in that: described step 2) in, in sulphonator, pass into SO
2, or add H
2sO
3carry out sulfonation processing.
8. the method for utilizing papermaking wastewater neutral and alkali black liquor to make cement grinding aid according to claim 6, is characterized in that: in described step 3), the time of anaerobic fermentation processing is 10--20 days; The temperature of anaerobic fermentation is 35--45 DEG C.
9. make the method for cement grinding aid according to the papermaking wastewater neutral and alkali black liquor that utilizes described in claim 6 or 7, it is characterized in that: described anaerobic fermentation device is connected with boiler, produces CH in anaerobic fermentation process
4, by CH
4lead to boiler boiler is heated, the hot water of boiler heating leads to anaerobic fermentation device; The temperature of hot water is controlled at 40--50 DEG C.
10. the method for utilizing papermaking wastewater neutral and alkali black liquor to make cement grinding aid according to claim 6, it is characterized in that: in described step 6), be finished product after adding in proportion urea, triethanolamine, ethylene glycol, acetic acid fully to stir according to the content of lignosulfonates in filtrate.
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| CN105198262A (en) * | 2015-09-11 | 2015-12-30 | 江苏锦宇环境工程有限公司 | Method for preparing efficient concrete water reducing agent by utilizing papermaking black liquid |
| CN106242340A (en) * | 2016-08-16 | 2016-12-21 | 仇颖莹 | A kind of preparation method of multicomponent biological matter cement grinding aid |
| CN106242350A (en) * | 2016-08-31 | 2016-12-21 | 苏州市湘园特种精细化工有限公司 | A kind of cement grinding aid |
| CN108014909A (en) * | 2016-10-28 | 2018-05-11 | 湖南昌迪环境科技有限公司 | The method and mineral products grinding aid of a kind of mineral products grinding |
| CN109020300A (en) * | 2018-09-28 | 2018-12-18 | 南宁博嘉新建材科技有限公司 | A kind of cement grinding aid and preparation method thereof |
| CN109777353A (en) * | 2019-03-22 | 2019-05-21 | 泉州欧米克生态建材科技有限公司 | A kind of clay grinding aid and preparation method thereof |
| CN110615637A (en) * | 2019-09-10 | 2019-12-27 | 广西喜华园建材科技有限公司 | Efficient cement grinding aid and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944486A (en) * | 2015-07-20 | 2015-09-30 | 周俊云 | Multifunctional sewage or waste water treatment equipment |
| CN105198262A (en) * | 2015-09-11 | 2015-12-30 | 江苏锦宇环境工程有限公司 | Method for preparing efficient concrete water reducing agent by utilizing papermaking black liquid |
| CN106242340A (en) * | 2016-08-16 | 2016-12-21 | 仇颖莹 | A kind of preparation method of multicomponent biological matter cement grinding aid |
| CN106242350A (en) * | 2016-08-31 | 2016-12-21 | 苏州市湘园特种精细化工有限公司 | A kind of cement grinding aid |
| CN108014909A (en) * | 2016-10-28 | 2018-05-11 | 湖南昌迪环境科技有限公司 | The method and mineral products grinding aid of a kind of mineral products grinding |
| CN108014909B (en) * | 2016-10-28 | 2020-05-15 | 湖南昌迪环境科技有限公司 | Mineral product grinding method and mineral product grinding aid |
| CN109020300A (en) * | 2018-09-28 | 2018-12-18 | 南宁博嘉新建材科技有限公司 | A kind of cement grinding aid and preparation method thereof |
| CN109777353A (en) * | 2019-03-22 | 2019-05-21 | 泉州欧米克生态建材科技有限公司 | A kind of clay grinding aid and preparation method thereof |
| CN110615637A (en) * | 2019-09-10 | 2019-12-27 | 广西喜华园建材科技有限公司 | Efficient cement grinding aid and preparation method thereof |
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