CN1138847C - Humic acid additives for water-coal slurry and its preparing process - Google Patents
Humic acid additives for water-coal slurry and its preparing process Download PDFInfo
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- CN1138847C CN1138847C CNB991159292A CN99115929A CN1138847C CN 1138847 C CN1138847 C CN 1138847C CN B991159292 A CNB991159292 A CN B991159292A CN 99115929 A CN99115929 A CN 99115929A CN 1138847 C CN1138847 C CN 1138847C
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Abstract
The present invention relates to humic acid type coal slurry additives and a preparation method thereof. The preparation process comprises that products with high surface activity, namely the coal slurry additives with a good slurry-forming property and a low price, are prepared from humic acid materials by oxidative degradation, sulfonation, methylation and modification. The present invention has the distinctive characteristic that the additives with different functions can be prepared through regulating the proportion and the dosage of a sulfonation agent and a methylation agent so as to satisfy the requirements of the slurry formation of the coal with different coalification degrees, and the additives can be used for pressurizing type gasification of coal slurry, boiler combustion, pipeline transportation of the same types of coal, etc.
Description
The present invention relates to a kind of preparation method of humic acid additives for water-coal slurry.
COAL-WATER SLURRY TECHNOLOGY is sophisticated Coal Chemical Industry new technology, and along with the popularization and the development of this technology, the research and development of slurries additive agent is active day by day, constantly has new additive to release.According to its purposes, additive can be divided into dispersion agent, stablizer and auxiliary agent.Dispersion agent makes each coal grain of coal slurry system be mutual dispersed, and slurry viscosity reduces, good fluidity; And stablizer makes that the coal grain is suspended in the not sedimentation or the settling velocity that slows down in the water in the slurry, and the effect of the two is of equal importance.Additive mainly is the tensio-active agent of some different performances, as organic polymer, polyose and Fatty Alcohol(C12-C14 and C12-C18), its effect is to reduce viscosity of coal slurry, increase stability, has now found that such as nearly hundred kinds of compounds such as poly-ethoxy alkyl nonionic surface active agent, poly-ethoxyalkyl phenol sulfonate.Organic sulfonate and carboxylate salt pulping are effective, and are easy to get, and are listed in the additive types of focus development.Now formed commercial additive kind and divided three major types: the first kind is a naphthalene sulfonic salt, as Co-Al board slurries additive agent; Second class is sulfonated lignin (US4104035); The 3rd class is a humic acid additives for water-coal slurry.Naphthalene sulfonic salt sludge forming performance is good, but costs an arm and a leg; Sulfonated lignin are widely used, but stability is not good enough; Humic acid additives for water-coal slurry, as EP293024A2 report be primary and the ethoxy alkylation modification thing of regeneration humic acids is made slurries additive agent, the US4502868 report be that brown coal are through NH
3H
2O alkalization, band are pressed with sulfurous gas (SO
2) sulfonation produces additive, these two kinds of humic acid activity things will prepare the good coal water slurry of comprehensive slurry performance all as the dispersion agent usefulness of coal water slurry, need composite special stablizer.Yi Shang many single additive does not all satisfy the requirement of China's industry slurrying on price and performance in a word.
The object of the invention is to overcome the deficiency that has additive now, and the novel water-coal-slurry additive that a kind of coal adaptability is strong, of high quality and at a reasonable price, produce simply, take into account dispersion and stable double effects is provided.
For achieving the above object, technical scheme of the present invention is: utilize inexpensive Sodium salts humic acids, through oxidative degradation, sulfonation reaction and methylation reaction, make and introduce more amphiphilic group on the humic acids molecular chain, be added in the slurry, the bonding action of the amphiphilic group by the humic acids molecular chain forms network structure, plays good dispersion and stable double effects.
Realize that main process of the present invention is:
1. granularity adds I in proportion for Sodium salts humic acids and oxidative degradation agent less than 0.2mm
#In the reactor, (stir to satisfy and form approximate homogeneous phase suspensoid) under the agitation condition, react 2.5h under 85 ℃ temperature, oxidative degradation agent/Sodium salts humic acids is 3～1;
2. the reaction feed liquid is delivered in the pressure filter through corrosion protection pump and is filtered pressure≤2kg/cm
3, press filtration 10min, water washes once, and water/Sodium salts humic acids is 2.5;
3. filter cake drops into II
#In the reactor, add water, neutralizing agent successively, carry out neutralization reaction, stir neutralization reaction liquid 10min, water/Sodium salts humic acids is 1.5, and neutralizing agent/Sodium salts humic acids is 0.05～0.4;
4. continue to II
#Add sulphonating agent, methylating reagent in the reactor, sulfonation reaction, methylation reaction 2.5h under 105 ℃ temperature, sulphonating agent/Sodium salts humic acids is 0.07～0.3, methylating reagent/Sodium salts humic acids is 0.01～0.01, at last reaction product is sent in the pan tank, or drying becomes solid product.
Implementing prescription of the present invention is: (in Sodium salts humic acids)
| Reaction process | Title feeds intake | Proportioning |
| Oxidative degradation | Sodium salts humic acids | 100 |
| The oxidative degradation agent | 100～150 | |
| N-process | Sodium hydroxide | 5～40 |
| Sulfonation process | Sulphonating agent | 7～30 |
| Process methylates | Methylating reagent | 1～10 |
Manufacturing the used main raw material of slurries additive agent is Sodium salts humic acids.
Manufacture the used oxidative degradation agent of slurries additive agent and select nitric acid for use, sulphonating agent is selected seven water S-WATs for use, and methylating reagent is selected formaldehyde for use, and neutralizing agent is selected sodium hydroxide for use.
Slurries additive agent provided by the invention is being taken into account and is being disperseed and stable double effects, depends merely on this a kind of additive, can prepare the more excellent coal water slurry of comprehensive slurry performance, and addition is little, does not need composite other auxiliary agent.Utilize this operational path, regulate the consumption proportion of sulfonation reaction and methylation reaction, can prepare the additive of different performance and purposes, satisfy the needs that different coals prepare high density, low viscosity, good fluidity coal water slurry.
Slurries additive agent provided by the invention, its pulping effect shows as: the water coal slurry concentration improvement value is 3～8%, (comparing with blank sample); Viscosity≤2000mPa.s, D=15.89 (S
-1); Stability of coal slurry≤2.0% (static bleed rate, %), flowability≤60S (gravity flow), rheological is yield pseudoplasticity.
By slurries additive agent provided by the invention, but adapt to coal bituminous coal, hard coal or other carbon containing, hydrogen solid matter and their composition of pulping, the coal water slurry of preparing can be widely used in the pipe-line transportation of pressurized gasification, boiler combustion and solid coal.Utilize this prescription can make the concentration of coal water slurry reach 72%, ton slurry cost is below 15 yuans.
The present invention is further illustrated in conjunction with evaluation result, but the invention is not restricted to present embodiment.
Example one
I
#The charge ratio of additive is: Sodium salts humic acids 100g, 20% nitric acid 125g, sodium hydroxide 12g, seven water S-WAT 18g, 37% formaldehyde 1.1ml, operating process is with above-mentioned technological process.The I that manufactures
#Additive pulping effect sees Table 1.
Table 1 I
#Additive pulping effect
I
#Additive lays particular emphasis on the dispersion effect, and the fluidity of slurry of preparation is good, and viscosity is low, the coal that suitable sludge forming performance is more stable.
Example two
II
#The charge ratio of additive is: Sodium salts humic acids 100g, 20% nitric acid 125g, sodium hydroxide 12g, seven water S-WAT 10g, 37% formaldehyde 2.0ml, operating process is with above-mentioned technological process.The II that manufactures
#Additive pulping effect sees Table 2.
Table 2 II
#Additive pulping effect
II
#Additive lays particular emphasis on stable effect, and the slurry stability of preparation is good, is fit to pulping dispersiveness coal preferably.
Example three
III
#The charge ratio of additive is: Sodium salts humic acids 100g, 20% nitric acid 125g, sodium hydroxide 12g, seven water S-WAT 14g, 37% formaldehyde 1.5ml, operating process is with above-mentioned technological process.The III that manufactures
#Additive pulping effect sees Table 3.
Table 3III
#Additive pulping effect
III
#Additive has been introduced the amphiphilic group of relative equilibrium on the molecular chain, in the slip system, the bonding action by the amphiphilic group on the humic acids molecular chain has formed the slurry internal network structure, and it is good dispersed and stable that slip is shown.
Claims (1)
1. the preparation method of a humic acid additives for water-coal slurry is characterized in that: to Sodium salts humic acids carry out oxidative degradation, sulfonation, the modification that methylates handles, the granularity of used Sodium salts humic acids is 0～0.3mm, HA 〉=35%; Sodium salts humic acids oxidative degradation temperature is 50～95 ℃, and the time is 1.0～3.0h, and the oxidative degradation agent is selected for use is 20% nitric acid, salpeter solution/Sodium salts humic acids=3～1; Filter the back filter cake is neutralized, what neutralization was selected for use is sodium hydroxide, sodium hydroxide/Sodium salts humic acids=0.05～0.3; Carry out sulfonation, methylation reaction 1～3.0h when being warming up to 60～100 ℃, what sulphonating agent was selected for use is seven water S-WATs, methylating reagent is selected for use is 37% formaldehyde, sulphonating agent/Sodium salts humic acids=0.01～0.3, methylating reagent/Sodium salts humic acids=0.001～0.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991159292A CN1138847C (en) | 1999-12-06 | 1999-12-06 | Humic acid additives for water-coal slurry and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991159292A CN1138847C (en) | 1999-12-06 | 1999-12-06 | Humic acid additives for water-coal slurry and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1298927A CN1298927A (en) | 2001-06-13 |
| CN1138847C true CN1138847C (en) | 2004-02-18 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007124681A1 (en) * | 2006-04-24 | 2007-11-08 | Guangzhou Devotion Thermal Technology Co., Ltd. | Desulfurizing coke-water slurry and process for preparation thereof |
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|---|---|---|---|---|
| CN101805653A (en) * | 2009-02-16 | 2010-08-18 | 李欣柏 | XB type coal saving agent |
| CN101560421B (en) * | 2009-04-20 | 2012-07-04 | 安徽理工大学 | High-concentration desulfurized coal water mixture additive and preparation method thereof |
| CN101812338A (en) * | 2010-04-28 | 2010-08-25 | 陕西科技大学 | Coal water slurry addition agent, preparation method thereof and coal water slurry based on same |
| CN103951835B (en) * | 2014-04-18 | 2015-12-02 | 陕西科技大学 | A kind of polyaldehyde is cross-linked the preparation method of sulfomethylation humic acids coal water slurry dispersing agent |
| CN103951836B (en) * | 2014-04-18 | 2016-01-20 | 陕西科技大学 | A kind of preparation method of sulfonated polycondensation modified humic acid coal water slurry dispersing agent |
| CN109280566A (en) * | 2018-11-08 | 2019-01-29 | 广西科技大学 | A method of using bagasse as the extensive producing synthesis gas of raw material |
| CN113322051A (en) * | 2021-06-29 | 2021-08-31 | 上海臻衍生物科技有限公司 | Environment-friendly high-temperature-resistant salt-resistant weathered coal drilling anti-collapse agent |
-
1999
- 1999-12-06 CN CNB991159292A patent/CN1138847C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007124681A1 (en) * | 2006-04-24 | 2007-11-08 | Guangzhou Devotion Thermal Technology Co., Ltd. | Desulfurizing coke-water slurry and process for preparation thereof |
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| CN1298927A (en) | 2001-06-13 |
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