CN104818063A - Coal water slurry additive and application thereof - Google Patents
Coal water slurry additive and application thereof Download PDFInfo
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- CN104818063A CN104818063A CN201510248740.1A CN201510248740A CN104818063A CN 104818063 A CN104818063 A CN 104818063A CN 201510248740 A CN201510248740 A CN 201510248740A CN 104818063 A CN104818063 A CN 104818063A
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Abstract
The invention discloses a coal water slurry additive which is composed of 20-40 wt% of water reducing agent, 20-35 wt% of lignosulfonate, 20-35 wt% of inorganic alkali, 2-20 wt% of ethylene glycol, 2-15 wt% of sodium metasilicate pentahydrate and 1-10 wt% of carboxymethyl cellulose. Besides, the invention also discloses application of the coal water slurry additive in preparing a coal water slurry. The coal water slurry additive can promote the disperse phase (coal particles) to be uniformly dispersed in the dispersion medium (water), and can effectively enhance the hydrophilicity of the coal and the electrostatic repulsion among the coal particles. The prepared coal water slurry has the advantages of higher coal content (or concentration), low viscosity, low bleeding rate, high flowability and high stability. Compared with the traditional formula, the coal water slurry additive can lower the slurry making cost by more than 20%.
Description
Technical field
The invention belongs to coal chemical technology, relate to a kind of slurries additive agent and uses thereof.
technical background:
Coal water slurry is a kind of novel coal based fluid fuel, and by the coal of about 60% ~ 70%, the water of about 30% ~ 40% and a small amount of additive form through certain technical process addition.It had both remained the original physical features of coal; Simultaneously there is again the same mobility of oil and stability, can store, pumping, atomization and stable burning; In addition its cheap price is a kind of more satisfactory for oily Coal Clean fuel.Coal water slurry is widely used in Industrial Boiler, Industrial Stoves and station boiler, for oil, for gas, for coal combustion; Also can be used as gasified raw material, for the production of synthetic ammonia and synthesizing methanol etc., can effectively reduce dust pollution, protosulphide and emitting nitride.But coal is lyophobic dust, coal water slurry belongs to coarse particles suspensoid, even easy slurrying coal have the size-grade distribution of high deposition efficiency, is also difficult to pulping, seriously constrains the application of COAL-WATER SLURRY TECHNOLOGY.
For ensureing normal use, coal water slurry is needed to have lower viscosity, lower syneresis rate, preferably mobility and stability; Consider based on atomization and efficiency of combustion and economic factors simultaneously, usually require that coal water slurry has the higher slurrying cost containing coal amount and reduction.In coal water slurry, add additive is the effective ways solved the problem, and particularly to the preparation of high density and high-stability coal water slurry, the selection of additive types and content thereof is particularly crucial.In addition, in coal water slurry, the cost of additive is only second to coal particles, and the proportioning difference of additive also can cause its price there are differences, so preparing rational additive formulations is the important channel controlling coal water slurry production cost.
At present, researching and developing different by its chemical constitution with the slurries additive agent used both at home and abroad, be divided into following a few class: the first, naphthalenesulfonate condensation compound.The advantage of this kind of additive has 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.The second, sulfonated lignin.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, is difficult to when being used alone meet industrial application requirement.3rd, humate.The advantage of this kind of additive is that dispersing property is good, but it belongs to ion-sensitive to underwater gold, easily forms precipitation, and slurry stability is poor.4th, poly carboxylic acid series.The advantage of this kind of additive is fluidity of slurry and good stability, but price is higher, and use range is narrower.5th, polyolefin series.The advantage of this kind of additive has stably dispersing effect for low-ash coal water slurry, but price is higher.
For the above-mentioned shortcoming of single coal water slurry, the composite additive of polycomponent is used to become current study hotspot.Such as, Chinese patent application CN101747964 A discloses a kind of good stability, high density and low viscous coal water slurry; Wherein additive comprises dispersion agent and stablizer, and described dispersion agent is the polyoxyethylene octylphenol ether dispersion agent of sodium lignosulfonate, Sodium dodecylbenzene sulfonate, thionamic acid class or EP=10, and described stablizer is carboxymethyl cellulose.Chinese patent application CN103509617 A discloses the special composite slurries additive agent of a kind of gasification, each component is by following weight proportion relation mixed preparing: the sulfonated lignin of 30 ~ 75%, the sulfonate and formaldehyde condenses of 10 ~ 45%, the polyethenoxy ether class of 5 ~ 15%, the phosphoric acid salt of 5 ~ 25%, the acid-base modifier of 0 ~ 5%, the stablizer of 0 ~ 2%.But these composite slurries additive agents still expose various problems and deficiency, mainly the viscosity of coal water slurry, syneresis rate, mobility and stability and efficiency of combustion unsatisfactory; The scope of application is narrower simultaneously, or large usage quantity causes cost higher.Therefore, in the urgent need to slurries additive agent that the polycomponent developing a kind of new low cost is composite.
Summary of the invention
For the above-mentioned defect of prior art, the invention provides the slurries additive agent that a kind of polycomponent is composite.After adding additive of the present invention, prepared coal water slurry has lower viscosity, lower syneresis rate, preferably mobility and stability; There is the higher slurrying cost containing coal amount (or concentration) and reduce simultaneously.
For this reason, the present invention takes following technical proposal: a kind of slurries additive agent, is characterized in that: be made up of water reducer, sulfonated lignin, mineral alkali, ethylene glycol, metasilicate pentahydrate sodium and carboxymethyl cellulose; Each component concentration is as follows: water reducer 20-40 wt%; Sulfonated lignin 20-35 wt%; Mineral alkali 20-35 wt%; Ethylene glycol 2-20 wt%; Metasilicate pentahydrate sodium 2-15 wt%; And carboxymethyl cellulose 1-10 wt%.
In one preferred embodiment, each component concentration of slurries additive agent is as follows: water reducer 23-37 wt%; Sulfonated lignin 22-32 wt%; Mineral alkali 22-32 wt%; Ethylene glycol 3-18 wt%; Metasilicate pentahydrate sodium 2-12 wt%; And carboxymethyl cellulose 1-8 wt%.
In a further preferred embodiment, each component concentration of slurries additive agent is as follows: water reducer 25-35 wt%; Sulfonated lignin 25-30 wt%; Mineral alkali 25-30 wt%; Ethylene glycol 5-15 wt%; Metasilicate pentahydrate sodium 2-8 wt%; And carboxymethyl cellulose 1-5 wt%.
In a concrete embodiment, each component concentration of slurries additive agent is as follows: water reducer 29 wt%; Sulfonated lignin 27 wt%; Mineral alkali 27 wt%; Ethylene glycol 9 wt%; Metasilicate pentahydrate sodium 5 wt%; And carboxymethyl cellulose 3 wt%.
Water reducer can be methanonaphthalene sulfonate, methylene-bis methyl naphthalene sulfonic acid salt, sulfonated alkyl naphathalene or naphthalenesulfonate, and their formaldehyde condensation products.In a concrete embodiment, described water reducer is naphthalenesulfonate formaldehyde condensation compound.
Sulfonated lignin can be sodium lignosulfonate, calcium lignin sulphonate, lignosulfonic acid potassium or ammonium lignosulphonate etc.In a concrete embodiment, described sulfonated lignin are sodium lignosulfonates.
Mineral alkali can be sodium hydroxide, potassium hydroxide, ammonium hydroxide or calcium hydroxide etc.; Be preferably sodium hydroxide.In a concrete embodiment, described mineral alkali is ion film caustic soda, sheet alkali or its combination.Preferably, described mineral alkali is the combination of ion film caustic soda and sheet alkali.
Ethylene glycol is conducive to the interfacial tension and the hydrophobe character that change coal particles surface; And can promote that water reducer and sulfonated lignin and coal particles surface adsorption point are evenly distributed, play the dispersion effect of dispersion agent to greatest extent.Contriver finds, when not making spent glycol, the stability of coal water slurry significantly reduces.
Metasilicate pentahydrate sodium has diluting effect, can increase the surface charge density of micelle in coal water slurry, thus increases electrostatic double layer and ζ-potential, and the repulsive force between particle is strengthened.Meanwhile, the silicate anion contained by Starso can with Ca in coal water slurry
2+, Mg
2+generate indissoluble thing Deng harmful ion, promote Na
+exchange interaction, the viscosity of coal water slurry is reduced, and mobility increase.
Carboxymethyl cellulose, together with ethylene glycol, further increases the stability of coal water slurry, and is conducive to reducing syneresis rate.Found by contrast experiment, not easily bleed, stability are strong to add the coal water slurry of carboxymethyl cellulose.
Slurries additive agent of the present invention can be made into the aqueous solution of any concentration, joins in rod mill, ball mill or agitation vat in the form of a solution; Also can make solid powder mixture, join in powder form in ball mill or rod mill.In one preferred embodiment, slurries additive agent of the present invention is faint yellow or brown solid powdery product, and effective content is 100%, has good integration, compatibleness and water-soluble; And transport, deposit conveniently, particularly winter is without the need to insulation, can prepare use at any time.
On the other hand, present invention also offers the purposes of a kind of slurries additive agent for the preparation of coal water slurry, it is characterized in that: described slurries additive agent of the present invention is made solid powder mixture or is made into the aqueous solution of any concentration, then add butt coal dust and appropriate water stirs, make coal water slurry.Wherein, the consumption of slurries additive agent is the 0.1-2 wt% of coal water 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 disperse phase (coal particle) is dispersed in dispersion medium (water); And more effectively can improve the wetting ability of coal and strengthen the electrostatic repulsion of coal intergranular.
(2) coal water slurry of the present invention has higher containing coal amount (or concentration); There is low viscosity, low syneresis rate, high workability and high stability simultaneously.
(3) compared with conventional formulation, slurries additive agent of the present invention has the slurrying cost of reduction, and amplitude can reach more than 20%.
Accompanying drawing explanation
Fig. 1 is slurries production technology schema.
Embodiment
Form with preferred implementation provides by object/of the present invention or scheme.For the understanding of the present invention to the explanation of these embodiments, and unrestricted feasible alternate manner, these other feasible embodiments can be learnt by practice of the present invention.
Below by embodiment, the present invention is further elaborated, but obvious scope of the present invention is not limited in following examples.
Embodiments of the invention and comparative example slurries production technology all conveniently carries out, and technical process as shown in Figure 1.
First, take the embodiment of the present invention of formula ratio and the additive of comparative example and water and join in medicament barrel, stir, make the additive aqueous solution.Using ball mill, under specified speed, by controlling the different coal-grinding time, obtaining 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 coal water slurry.Original coal water slurry is pumped into colour strainer process after vibratory screening apparatus slagging-off.Coal water slurry after process and optional stabiliser solution join in stable bucket and again stir.And then carry out strengthening shearing and homogeneous slaking, obtain finished product coal water slurry, be finally pumped in slurry can.Sampling is all carried out in homogeneous slaking tank.The properties test of coal water slurry is carried 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.In addition, the various chemical used are commercially available prod.
embodiment 1
The coal sample place of production: the prosperous ore deposit of Yanzhou coalfield.Index of correlation: ash content (9%); Sulphur content (0.48); Thermal value (6557 kcal/kg); Total water is 5.9%; Hardgrove grindability is 60.
According to the technical process production coal water slurry 290 tons shown in Fig. 1; Wherein feed coal 199 tons, additive 1.015 tons, 90 tons, water.The composition of additive is as shown in table 1.The properties of made coal water 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 coal water slurry is as shown in table 2.
comparative example 1
Repeat the step of embodiment 1, but the stablizer used is ferrous sulfate, and stablizer add difference on opportunity.The stablizer of comparative example 1 adds in stable bucket; Embodiment 1 is then direct composite, no longer adds in stable bucket link.The composition of additive and the properties of made coal water 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 coal water 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 lignosulfonate | 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% |
As can be seen from Table 2, compared with prior art, use the viscosity in aqueous coal slurries obtained by slurries additive agent of the present invention lower the higher of concentration 65% containing under coal amount, reach secondary slurry standard; The static syneresis rate of 24 hours is starkly lower than 3% required by industry standard, and obvious bleed all appears in the coal water slurry surface of comparative example 1-3.Coal water slurry slurry performance of the present invention is good, and fluidity of slurry is good; And coal particle is dispersed in dispersion medium (water), and combustion efficacy is obviously better.In addition, water coal slurry stability of the present invention is good, not stratified in 30 days, without precipitation; Not stratified in 60 days, without expendable hard-caked sediment.Therefore, transport, deposit conveniently, particularly winter is without the need to insulation, can prepare use at any time.
The coal water slurry performance of table 2 embodiment 1-3 and comparative example 1-3
On the other hand, contrasted by table 3, can obviously find out has obvious gap on addition and reagent combination, relative to conventional formulation and other brand pharmaceutical products of market, patent formulation more can adapt to the need of production of local coal, and reduces costs 23 about percent.In addition, it is pointed out that ferrous sulfate in conventional formulation is as a kind of stablizer, can only add after ball mill grinding in the technical process of Fig. 1, this addition manner not only can increase the complicacy of operation, also can cause and melt not exclusively with slurry, easily forms coal water slurry caking; And 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 stablizer, namely production process is simplified, fully mix after coal grain and medicament can be allowed again to stir in ball mill, pulping rear stability is high.
Table 3 reagent combination price comparison shows
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.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., be all included within protection scope of the present invention.
Claims (9)
1. a slurries additive agent, is characterized in that: be made up of water reducer, sulfonated lignin, mineral alkali, ethylene glycol, metasilicate pentahydrate sodium and carboxymethyl cellulose; Each component concentration is as follows: water reducer 20-40 wt%; Sulfonated lignin 20-35 wt%; Mineral alkali 20-35 wt%; Ethylene glycol 2-20 wt%; Metasilicate pentahydrate sodium 2-15 wt%; And carboxymethyl cellulose 1-10 wt%.
2. slurries additive agent according to claim 1, wherein, each component concentration is as follows: water reducer 23-37 wt%; Sulfonated lignin 22-32 wt%; Mineral alkali 22-32 wt%; Ethylene glycol 3-18 wt%; Metasilicate pentahydrate sodium 2-12 wt%; And carboxymethyl cellulose 1-8 wt%.
3. slurries additive agent according to claim 2, wherein, each component concentration is as follows: water reducer 25-35 wt%; Sulfonated lignin 25-30 wt%; Mineral alkali 25-30 wt%; Ethylene glycol 5-15 wt%; Metasilicate pentahydrate sodium 2-8 wt%; And carboxymethyl cellulose 1-5 wt%.
4. slurries additive agent according to claim 3, wherein, each component concentration is as follows: water reducer 29 wt%; Sulfonated lignin 27 wt%; Mineral alkali 27 wt%; Ethylene glycol 9 wt%; Metasilicate pentahydrate sodium 5 wt%; And carboxymethyl cellulose 3 wt%.
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 sulfonated lignin are sodium lignosulfonates.
7. slurries additive agent according to claim 1, wherein, described mineral alkali is the combination of ion film caustic soda and sheet alkali.
8. a slurries additive agent is for the preparation of the purposes of coal water slurry, it is characterized in that: slurries additive agent described in claim 1 is made solid powder mixture or be made into the aqueous solution of any concentration, then add butt coal dust and appropriate water stirs, make coal water slurry.
9. purposes according to claim 8, wherein, the consumption of slurries additive agent is the 0.1-2 wt% of coal water slurry gross weight.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567356A (en) * | 2016-01-15 | 2016-05-11 | 欣格瑞（山东）环境科技有限公司 | Synthetic process and application of coal water slurry additive |
| CN106010686A (en) * | 2015-12-19 | 2016-10-12 | 济南源盛化工科技有限公司 | Coal water slurry additive |
| 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 |
| CN114160306A (en) * | 2021-11-18 | 2022-03-11 | 万华化学（宁波）有限公司 | Preparation method of polar high-molecular type coal water slurry additive and residual carbon separation method |
| CN114479970A (en) * | 2022-03-01 | 2022-05-13 | 北京时代思动科技有限公司 | Low-doping water coal slurry additive and preparation method thereof |
| 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 |
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| CN101747964A (en) * | 2010-01-22 | 2010-06-23 | 浙江大学 | Water coal slurry and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106010686A (en) * | 2015-12-19 | 2016-10-12 | 济南源盛化工科技有限公司 | Coal water slurry additive |
| CN105567356A (en) * | 2016-01-15 | 2016-05-11 | 欣格瑞（山东）环境科技有限公司 | Synthetic process and application of coal water slurry additive |
| 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 |
| CN114160306A (en) * | 2021-11-18 | 2022-03-11 | 万华化学（宁波）有限公司 | Preparation method of polar high-molecular type coal water slurry additive and residual carbon separation method |
| 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 |
| CN114479970A (en) * | 2022-03-01 | 2022-05-13 | 北京时代思动科技有限公司 | Low-doping water coal slurry additive and preparation method thereof |
| 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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Address after: 273100 Chongwen Avenue, Qufu, Jining, Shandong 106 Patentee after: Qufu three clean energy Limited by Share Ltd Address before: 273100, No. 168, South Chongwen Road, Mausoleum Town, Jining, Shandong, Qufu Patentee before: Qufu three allows coal water slurry company limited |