CN104818063B - Slurries additive agent and application thereof - Google Patents
Slurries additive agent and application thereof Download PDFInfo
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- CN104818063B CN104818063B CN201510248740.1A CN201510248740A CN104818063B CN 104818063 B CN104818063 B CN 104818063B CN 201510248740 A CN201510248740 A CN 201510248740A CN 104818063 B CN104818063 B CN 104818063B
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Abstract
The invention discloses a kind of slurries additive agent, be made up of water reducer, lignosulfonates, inorganic base, ethylene glycol, metasilicate pentahydrate sodium and carboxymethyl cellulose; Each constituent content is as follows: water reducer 20-40wt%; Lignosulfonates 20-35wt%; Inorganic base 20-35wt%; Ethylene glycol 2-20wt%; Metasilicate pentahydrate sodium 2-15wt%; And carboxymethyl cellulose 1-10wt%. Additionally, the invention also discloses a kind of slurries additive agent for preparing the purposes of water-coal-slurry. The slurries additive agent of the present invention can not only promote that dispersion phase (coal particle) is dispersed in disperse medium (water); And more can be effectively improved the hydrophilic of coal and strengthen the electrostatic repulsion of coal intergranular; Made water-coal-slurry has higher containing coal amount (or concentration); There is low viscosity, low syneresis rate, high fluidity and high stability simultaneously; Compared with conventional formulation, having the slurrying cost of reduction, amplitude is up to more than 20%.
Description
Technical field
The invention belongs to coal chemical technology, relate to a kind of slurries additive agent and application thereof.
Technical background:
Water-coal-slurry is a kind of novel coal based fluid fuel, the coal of about 60%��70%, the water of about 30%��40% and a small amount of additive form through certain technological process addition. It had both remained the original physical features of coal; There is again the same mobility of oil and stability, it is possible to store, pump, be atomized and smooth combustion simultaneously; In addition its cheap price, is a kind of more satisfactory generation oil Coal Clean fuel. Water-coal-slurry is widely used in Industrial Boiler, Industrial Stoves and station boiler, for oil, for gas, for coal combustion; Also as gasified raw material, can be used for producing synthesis ammonia and synthesizing methanol etc., be effectively reduced dust pollution, protosulphide and emitting nitride. But, coal is lyophobic dust, and water-coal-slurry belongs to coarse granule suspended substance, even easy slurrying coal there is the particle size distribution of high deposition efficiency, it is also difficult to pulping, seriously constrain the application of COAL-WATER SLURRY TECHNOLOGY.
For ensureing normal use, it is necessary to water-coal-slurry has relatively low viscosity, relatively low syneresis rate, good mobility and stability; It is simultaneously based on atomization and efficiency of combustion and economic factor considers, usually require that water-coal-slurry has the higher slurrying cost containing coal amount and reduction. Adding additive in water-coal-slurry is the effective ways solving the problems referred to above, and particularly the selection of the preparation to high concentration and high-stability coal water slurry, additive types and content thereof is particularly critical. Additionally, in water-coal-slurry, the cost of additive is only second to coal particles, and the proportioning difference of additive will also result in its price and there are differences, so preparing rational additive formulations is the important channel controlling water-coal-slurry production cost.
At present, researching and developing different by its chemical composition with the slurries additive agent used both at home and abroad, be divided into following a few class: first, naphthalenesulfonate condensation compound. The advantage of this kind of additive is to have good wetting and dispersing performance, and slurry flow pattern is good, applied widely;But slurry stability is poor, easy bleed and produce irreversible hard-caked sediment, and also on the high side. Second, lignosulfonates. The advantage of this kind of additive is that raw material sources are extensive, low price, and slurry stability is good; But material composition is complicated, unstable properties, it is difficult to when being used alone meet commercial Application requirement. 3rd, humate. The advantage of this kind of additive is that dispersive property is good, but underwater gold is belonged to ion-sensitive by it, it is easy to forming precipitation, slurry stability is poor. 4th, polycarboxylic acids series. The advantage of this kind of additive is fluidity of slurry and good stability, but price is higher, uses scope narrower. 5th, polyolefin series. The advantage of this kind of additive is to have stably dispersing effect for low-ash water-coal-slurry, but price is higher.
For the disadvantages mentioned above of single water-coal-slurry, the additive using multicomponent composite becomes current study hotspot. Such as, Chinese patent application CN101747964A discloses a kind of good stability, high concentration and low viscous water-coal-slurry; Wherein additive includes dispersant and stabilizer, and described dispersant is the OPEO dispersant of sodium lignin sulfonate, dodecylbenzene sodium sulfonate, sulfamic acid class or EP=10, and described stabilizer is carboxymethyl cellulose. Chinese patent application CN103509617A discloses the composite slurries additive agent that a kind of coal gasification is special, each component presses following weight proportion relation mixed preparing: the lignosulfonates of 30��75%, the sulfonate and formaldehyde condensation substance of 10��45%, the polyethenoxy ether class of 5��15%, the phosphate of 5��25%, the acid-base modifier of 0��5%, the stabilizer of 0��2%. But, these composite slurries additive agents still expose various problems and deficiency, and mainly the viscosity of water-coal-slurry, syneresis rate, mobility and stability and efficiency of combustion are unsatisfactory; The scope of application is narrower simultaneously, or large usage quantity causes relatively costly. Therefore, the slurries additive agent that multicomponent in the urgent need to developing a kind of new low cost is composite.
Summary of the invention
For the drawbacks described above of prior art, the invention provides the slurries additive agent that a kind of multicomponent is composite. When, after the additive adding the present invention, prepared water-coal-slurry has relatively low viscosity, relatively low syneresis rate, good mobility and stability; There is the higher slurrying cost containing coal amount (or concentration) and reduction simultaneously.
For this, the present invention takes following technical proposal: a kind of slurries additive agent, it is characterised in that: it is made up of water reducer, lignosulfonates, inorganic base, ethylene glycol, metasilicate pentahydrate sodium and carboxymethyl cellulose; Each constituent content is as follows: water reducer 20-40wt%; Lignosulfonates 20-35wt%; Inorganic base 20-35wt%; Ethylene glycol 2-20wt%; Metasilicate pentahydrate sodium 2-15wt%; And carboxymethyl cellulose 1-10wt%.
In one preferred embodiment, each constituent content of slurries additive agent is as follows: water reducer 23-37wt%; Lignosulfonates 22-32wt%; Inorganic base 22-32wt%; Ethylene glycol 3-18wt%; Metasilicate pentahydrate sodium 2-12wt%; And carboxymethyl cellulose 1-8wt%.
In a further preferred embodiment, each constituent content of slurries additive agent is as follows: water reducer 25-35wt%; Lignosulfonates 25-30wt%; Inorganic base 25-30wt%; Ethylene glycol 5-15wt%; Metasilicate pentahydrate sodium 2-8wt%; And carboxymethyl cellulose 1-5wt%.
In a specific embodiment, each constituent content of slurries additive agent is as follows: water reducer 29wt%; Lignosulfonates 27wt%; Inorganic base 27wt%; Ethylene glycol 9wt%; Metasilicate pentahydrate sodium 5wt%; And carboxymethyl cellulose 3wt%.
Water reducer can be methanonaphthalene sulfonate, di-2-ethylhexylphosphine oxide methyl naphthalene sulfonic acid salt, alkylnaphthalene sulfonate or naphthalene sulfonate, and their formaldehyde condensation products. In a specific embodiment, described water reducer is naphthalenesulfonate formaldehyde condensation compound.
Lignosulfonates can be sodium lignin sulfonate, calcium lignosulfonate, lignin sulfonic acid potassium or ammonium lignosulphonate etc. In a specific embodiment, described lignosulfonates are sodium lignin sulfonates.
Inorganic base can be sodium hydroxide, potassium hydroxide, ammonium hydroxide or calcium hydroxide etc.; It is preferably sodium hydroxide. In a specific embodiment, described inorganic base is ion film caustic soda, sheet alkali or its combination. Preferably, described inorganic base is ion film caustic soda and the combination of sheet alkali.
Ethylene glycol is conducive to changing interfacial tension and the hydrophobe character on coal particles surface; And can promote that water reducer and lignosulfonates and coal particles surface adsorption point are evenly distributed, play the dispersion effect of dispersant to greatest extent. Inventor have found that, when not making spent glycol, the stability of water-coal-slurry significantly reduces.
Metasilicate pentahydrate sodium has diluting effect, by increasing capacitance it is possible to increase the surface charge density of micelle in water-coal-slurry, thus increasing electric double layer and ��-potential, makes the repulsive force between particle strengthen. Meanwhile, the silicate anion contained by sodium metasilicate can with Ca in water-coal-slurry2+��Mg2+Generate indissoluble thing Deng harmful ion, promote Na+Exchange interaction, make the viscosity of water-coal-slurry reduce, and mobility increase.
Carboxymethyl cellulose, together with ethylene glycol, further increases the stability of water-coal-slurry, and advantageously reduces syneresis rate. Being found by contrast experiment, the interpolation water-coal-slurry not easily bleed of carboxymethyl cellulose, stability are strong.
The slurries additive agent of the present invention can be made into the aqueous solution of any concentration, joins in rod mill, ball mill or agitator in the form of a solution; Solid powder mixture can also be made, join in powder form in ball mill or rod mill. In one preferred embodiment, the slurries additive agent of the present invention is faint yellow or brown solid powdery product, and effective content is 100%, has good integration, compatibility and water solublity; And transporting, deposit conveniently, particularly winter is without insulation, can prepare use at any time.
On the other hand, present invention also offers a kind of slurries additive agent for preparing the purposes of water-coal-slurry, it is characterized in that: the described slurries additive agent of the present invention is made solid powder mixture or is made into the aqueous solution of any concentration, it is subsequently adding butt coal dust and appropriate water stirs, make water-coal-slurry. Wherein, the consumption of slurries additive agent is the 0.1-2wt% of water-coal-slurry gross weight.
Compared with prior art, the invention has the beneficial effects as follows:
(1) slurries additive agent of the present invention can not only promote that dispersion phase (coal particle) is dispersed in disperse medium (water); And more can be effectively improved the hydrophilic of coal and strengthen the electrostatic repulsion of coal intergranular.
(2) water-coal-slurry of the present invention has higher containing coal amount (or concentration); There is low viscosity, low syneresis rate, high fluidity and high stability simultaneously.
(3) compared with conventional formulation, the slurries additive agent of the present invention has the slurrying cost of reduction, and amplitude is up to more than 20%.
Accompanying drawing explanation
Fig. 1 is slurries production technology flow chart.
Detailed description of the invention
Form with preferred implementation is provided by purpose/of the present invention or scheme. Explanation to these embodiments is for the understanding of the present invention, and unrestricted feasible alternate manner, and these other feasible embodiments can be learnt by the practice of the present invention.
By the examples below the present invention is further elaborated, it is apparent that the scope of the present invention is not limited in following example.
Embodiments of the invention and comparative example slurries production technology all conventionally carry out, and technological process is as shown in Figure 1.
First, weigh the embodiment of the present invention of formula ratio and join in medicament barrel with the additive of comparative example and water, stir, make additive aqueous solution. Use ball mill, under rated speed, by controlling the different coal-grinding time, obtain the coal dust that granularity is different. The coal dust of the additive aqueous solution in medicament barrel and formula ratio is joined in Raw material pail. Subsequently, the mixture pump in Raw material pail is sent in ball mill and carries out defibrination, obtain original water-coal-slurry. Original water-coal-slurry is pumped into pulp filter after vibrosieve removes the gred and processes. Water-coal-slurry and optional stabiliser solution after process join in stable bucket and are again stirring for. Then carry out strengthening again to shear and homogeneous ripening, obtain product water coal slurry, be finally pumped in slurry can. Sampling all carries out in homogeneous ripening tank. The properties test of water-coal-slurry carries out according to standard GB/T/T18855-2002, GB/T18856.2-2002, GB/T18856.4-2002 and relevant industries standard, and this is well-known to those skilled in the art. It addition, the various chemicals used are commercially available prod.
Embodiment 1
The coal sample place of production: Yanzhou coalfield prosperity ore deposit. Index of correlation: ash (9%); Sulphur content (0.48); Caloric value (6557kcal/kg); Total moisture is 5.9%; Hardgrove grindability is 60.
Technological process shown in Fig. 1 produces water-coal-slurry 290 tons; Wherein feed coal 199 tons, additive 1.015 tons, 90 tons of water. The composition of additive is as shown in table 1. The properties of made water-coal-slurry is as shown in table 2. Percentages is all weight percentage numerical value.
Embodiment 2-3
Repeat the step of embodiment 1, except the composition of additive is different, as shown in table 1. The properties of made water-coal-slurry is as shown in table 2.
Comparative example 1
Repeat the step of embodiment 1, but the stabilizer used is ferrous sulfate, and the addition of stabilizer is different for opportunity. The stabilizer of comparative example 1 adds in stable bucket; Embodiment 1 is then directly composite, does not add in stable bucket link. The composition of additive and the properties of made water-coal-slurry are respectively as shown in Table 1 and Table 2.
Comparative example 2-3
Repeat the step of embodiment 1, except the composition of additive is different, as shown in table 1. The properties of made water-coal-slurry is as shown in table 2.
The slurries additive agent formula of table 1 embodiment 1-3 and comparative example 1-3
| Additive | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Naphthalenesulfonate formaldehyde condensation compound | 29% | 23% | 37% | 68% | 32% | 31% |
| Sodium lignin sulfonate | 27% | 32% | 22% | 12% | 29% | 29% |
| Ion film caustic soda | 9% | 10% | 7% | 7% | 9% | 10% |
| Sheet alkali | 18% | 19% | 7% | 9% | 18% | 22% |
| Ethylene glycol | 9% | 3% | 17% | 9% | ||
| Metasilicate pentahydrate sodium | 5% | 12% | 2% | 5% | ||
| Carboxymethyl cellulose | 3% | 1% | 8% | 3% | 3% | |
| Ferrous sulfate | 4% |
From table 2 it can be seen that compared with prior art, higher containing under coal amount in concentration 65%, the viscosity in aqueous coal slurries obtained by slurries additive agent using the present invention is relatively low, reaches two grades of slurry standards;The static syneresis rate of 24 hours is significantly lower than 3% required by industry standard, and obvious bleed all occurs in the water-coal-slurry surface of comparative example 1-3. The water-coal-slurry slurry performance of the present invention is good, and fluidity of slurry is good; And coal particle is dispersed in disperse medium (water), and combustion efficiency is substantially better. Additionally, the water coal slurry stability of the present invention is good, not stratified in 30 days, without precipitation; In 60 days not stratified, without expendable hard-caked sediment. Therefore, transporting, deposit conveniently, particularly winter is without insulation, can prepare use at any time.
The water-coal-slurry performance of table 2 embodiment 1-3 and comparative example 1-3
On the other hand, contrasted by table 3, it is evident that there is obvious gap on addition and reagent combination, relative to conventional formulation and other brand pharmaceutical products of market, patent formulation is suitable for the production needs of local coal, and reduces cost about percent 23. In addition it should be pointed out that, the ferrous sulfate in conventional formulation is as a kind of stabilizer, the technological process of Fig. 1 can only be added after ball mill grinding, this addition manner not only can increase the complexity of operation, also can cause and melt not exclusively with slurry, is easily formed water-coal-slurry caking; And the slurries additive agent formula of the present invention has discarded ferrous sulfate, improve formula, increase newly and make spent glycol, carboxymethyl cellulose, jointly add before entering ball mill with other medicament as stabilizer, namely production process is simplified, coal grain and medicament can be allowed again to be sufficiently mixed after stirring in ball mill, and pulping rear stability is high.
Table 3 reagent combination price comparison's table
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations. All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., be all contained within protection scope of the present invention.
Claims (8)
1. a slurries additive agent, it is characterised in that: it is made up of water reducer, lignosulfonates, inorganic base, ethylene glycol, metasilicate pentahydrate sodium and carboxymethyl cellulose; Each constituent content is as follows: water reducer 20-40wt%; Lignosulfonates 20-35wt%; Inorganic base 20-35wt%; Ethylene glycol 2-20wt%; Metasilicate pentahydrate sodium 2-15wt%; And carboxymethyl cellulose 1-10wt%.
2. slurries additive agent according to claim 1, wherein, each constituent content is as follows: water reducer 23-37wt%; Lignosulfonates 22-32wt%; Inorganic base 22-32wt%; Ethylene glycol 3-18wt%; Metasilicate pentahydrate sodium 2-12wt%; And carboxymethyl cellulose 1-8wt%.
3. slurries additive agent according to claim 2, wherein, each constituent content is as follows: water reducer 25-35wt%; Lignosulfonates 25-30wt%; Inorganic base 25-30wt%; Ethylene glycol 5-15wt%; Metasilicate pentahydrate sodium 2-8wt%; And carboxymethyl cellulose 1-5wt%.
4. slurries additive agent according to claim 3, wherein, each constituent content is as follows: water reducer 29wt%; Lignosulfonates 27wt%; Inorganic base 27wt%; Ethylene glycol 9wt%; Metasilicate pentahydrate sodium 5wt%; And carboxymethyl cellulose 3wt%.
5. slurries additive agent according to claim 1, wherein, described water reducer is naphthalenesulfonate formaldehyde condensation compound.
6. slurries additive agent according to claim 1, wherein, described lignosulfonates are sodium lignin sulfonates.
7. slurries additive agent according to claim 1, wherein, described inorganic base is ion film caustic soda and the combination of sheet alkali.
8. a slurries additive agent is for preparing the purposes of water-coal-slurry, it is characterized in that: slurries additive agent described in claim 1 is made solid powder mixture or is made into the aqueous solution of any concentration, it is subsequently adding butt coal dust and appropriate water stirs, make water-coal-slurry; Wherein, the consumption of slurries additive agent is the 0.1-2wt% of water-coal-slurry gross weight.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106010686A (en) * | 2015-12-19 | 2016-10-12 | 济南源盛化工科技有限公司 | Coal water slurry additive |
| CN105567356B (en) * | 2016-01-15 | 2017-07-28 | 欣格瑞（山东）环境科技有限公司 | A kind of synthesis technique of slurries additive agent and application |
| CN106118764A (en) * | 2016-06-22 | 2016-11-16 | 艾永生 | A kind of slurries additive agent |
| CN106867603A (en) * | 2017-02-28 | 2017-06-20 | 佛山市天亿化工有限公司 | A kind of sewage produces the additive of water-coal-slurry |
| CN108753387A (en) * | 2018-06-19 | 2018-11-06 | 曲阜三让洁能股份有限公司 | It is a kind of to produce coal water slurry process method using surface active agent wastewater |
| CN109777531A (en) * | 2018-12-24 | 2019-05-21 | 广州建盛建材有限公司 | A kind of naphthalene system coal water slurry dispersing agent and its application |
| CN110373942A (en) * | 2019-08-01 | 2019-10-25 | 曲阜三让洁能股份有限公司 | A kind of dedicated water-coal-slurry and preparation method thereof for producing black pigment |
| CN111534346A (en) * | 2020-05-29 | 2020-08-14 | 新沂市建科新材料有限公司 | Efficient environment-friendly coal water slurry additive and preparation process thereof |
| CN114160306B (en) * | 2021-11-18 | 2024-06-25 | 万华化学（宁波）有限公司 | Preparation method of polar polymer type coal water slurry additive and method for separating carbon residue |
| CN114540088A (en) * | 2022-01-06 | 2022-05-27 | 浙江石油化工有限公司 | Method for producing high-sulfur petroleum coke slurry additive |
| CN114479970B (en) * | 2022-03-01 | 2023-10-27 | 北京时代思动科技有限公司 | Preparation method of low-doping coal water slurry additive |
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| CN101747964A (en) * | 2010-01-22 | 2010-06-23 | 浙江大学 | Water coal slurry and preparation method thereof |
| CN103509617A (en) * | 2013-01-17 | 2014-01-15 | 湖南东盈煤化工技术开发有限公司 | Special composite coal water slurry additive for coal gasification |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747964A (en) * | 2010-01-22 | 2010-06-23 | 浙江大学 | Water coal slurry and preparation method thereof |
| CN103509617A (en) * | 2013-01-17 | 2014-01-15 | 湖南东盈煤化工技术开发有限公司 | Special composite coal water slurry additive for coal gasification |
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