CN102773079A - Method and system for coproducing sulfonated coal and humic acid by using sulfuric acid - Google Patents
Method and system for coproducing sulfonated coal and humic acid by using sulfuric acid Download PDFInfo
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Abstract
The invention relates to a method and system for coproducing sulfonated coal and humic acid by using sulfuric acid. The method comprises the following steps: mixing concentrated sulfuric acid and coal at the mass ratio of 2:1 to 6:1, and subjecting the mixture to reaction for 4-20 hours at 100-200 DEG C to obtain the sulfonated coal; adjusting the formed diluted acid solution into the 10-20% sulfuric acid solution, mixing the 10-20% sulfuric acid solution with the coal at the mass ratio of 1:1 to 2:1, and subjecting the mixture to reaction for 30-120 minutes at 40-80 DEG C to obtain the crude mixture of the humic acid, wherein the coal contains 30% of humic acid or more. The coal particles are sulfonated by the concentrated sulfuric acid to prepare the sulfonated coal, and then the washed waste acid solution is used for oxidizing the feed coal with the humic acid to increase the content of the humic acid in the feed coal. The problem on the discharge of the acid-containing wastewater is solved, and the economic benefit of enterprises is improved. In addition, according to the method, the waste heat of the industrial waste flue gas is fully utilized, and the energy-saving environmental-protection circular economy route is realized.
Description
Technical field
The present invention relates to the method for a kind of coproduction sulfonated coal and humic acid, particularly relate to a kind of method and system with sulfuric acid and coal coproduction sulfonated coal and humic acid.
Background technology
Sulfonated coal is that coal generation sulfonating reactions such as the concentrated sulfuric acid and bituminous coal, brown coal are processed.Sulfonated coal has that surface area is big, surface polarity is strong, adsorption capacity is good and have good characteristics such as ion-exchange activity, is widely used in and reclaims metal, preparation active carbon and organic reaction catalyst etc. in sewage cleaning agent, water softener, the hydrometallurgy.Sulfonated coal has ion-exchange and two effects of surface adsorption concurrently in water, it all has absorbability preferably to nitro compound, amino-compound, phenols, organochlorine, organophosphor etc.; In industries such as medicine, dyestuff, agricultural chemicals, be used to handle and contain phenol, fluorine-containing, the industrial wastewater that contains heavy metal ion and reclaim organic matter.Handle waste water with sulfonated coal, not only removed dark dense color, make water become clear, the chemical oxygen consumption (COC) of waste water, biochemical oxygen demand (BOD) are reduced.When producing sulfonated coal with the concentrated sulfuric acid, its product also has pickle except sulfonated coal, if pickle is directly discharged, can cause very big pollution to environment; If dilution heat of sulfuric acid is processed the concentrated sulfuric acid again through the absorption tower, production cost then can be very high.
Summary of the invention
The technical problem that the present invention will solve provides a kind of method with producing sulfuric acid and jointly sulfonated coal and humic acid; The residue dilution heat of sulfuric acid that can be enough produce behind the sulfonated coal is produced humic acid; Sulfuric acid is fully used, when having solved the acid-bearing wastewater discharging, has increased economic benefit.
The present invention comprises the following steps: with the method for producing sulfuric acid and jointly sulfonated coal and humic acid
A, the coal particles of granularity less than 30mm is provided;
B, be that the ratio of 2:1 ~ 6:1 joins in first reaction unit more than or equal to 50% sulfuric acid and the particle after the above-mentioned pulverizing according to mass ratio, stir, under 100 ~ 200 ℃ temperature conditions, reacted 4 ~ 20 hours concentration;
C, with equipment for separating liquid from solid with reacted separating substances, the solid that obtains is dried after washing, and obtains sulfonated coal;
D, the pickle that the liquid that obtains after the Separation of Solid and Liquid and washing back are formed are mixed; Adding water or sulfuric acid then, be adjusted to concentration and be 10% ~ 20% sulfuric acid solution, is that the ratio of 1:1 ~ 2:1 join in second reaction unit more than or equal to 30% humic acid material coal particle according to mass ratio with the sulfuric acid solution that obtains and humic acid content; Stir; Under 40 ~ 80 ℃ temperature conditions, reacted 30 ~ 120 minutes, obtain the humic acid crude mixture.
The present invention is with the method for producing sulfuric acid and jointly sulfonated coal and humic acid, and the alr mode of the reactant in wherein said step b and the steps d is that mechanical system stirs.
Preferably, the alr mode of the reactant among the said step b is that bubble type stirs, and feeds 100 ~ 300 ℃ waste gas in the bottom of reaction unit or activated coke is resolved 100 ~ 300 ℃ the parsing hot-air that the back forms.
Preferably, among the said step b, waste gas that feeds in the bottom of reaction unit or the temperature of resolving hot-air are 180 ~ 240 ℃.
The present invention is with the method for producing sulfuric acid and jointly sulfonated coal and humic acid, and the alr mode of the reactant in the wherein said steps d is that bubble type stirs, and feeds 50 ~ 120 ℃ useless flue gas in the bottom of reaction unit.
Preferably, in the said steps d, the useless flue gas after the useless flue gas that feeds in the bottom of reaction unit is dry brown coal, its temperature is 70 ~ 100 ℃.The fume afterheat utilization is one of energy-saving and cost-reducing main contents of China, and the present invention can recycle remaining acid pickle and waste heat behind the coproduction sulfonated coal simultaneously, and realization environmental protection, energy-conservation, economic benefit have realistic meaning.
The present invention is with the method for producing sulfuric acid and jointly sulfonated coal and humic acid, and among the wherein said step b, the mass ratio of sulfuric acid and particle is 3:1 ~ 5:1, under 150 ~ 175 ℃ temperature conditions, reacts 8 ~ 13 hours.
Preferably, the concentration of the sulfuric acid that reacts in the steps d is 16% ~ 19%, and the mass ratio of sulfuric acid solution and coal particles is 1:1 ~ 1.4:1, under 50 ~ 70 ℃ temperature conditions, reacts 40 ~ 60 minutes.
The present invention through input sulfuric acid and coal, can realize coproduction sulfonated coal and humic acid with the method for producing sulfuric acid and jointly sulfonated coal and humic acid; The concentration of sulfuric acid from high to low, the ladder utilization has made full use of acid ion; When solving the acid-bearing wastewater discharging, increased economic benefit.
Another problem that the present invention will solve provides a kind of system with producing sulfuric acid and jointly sulfonated coal and humic acid.
A kind of system of the present invention with producing sulfuric acid and jointly sulfonated coal and humic acid; Comprise crushing and screening device, first reaction unit, first solid-liquid separator, rinsing machine, first dryer, screening dust arrester, liquid dispensing device, second reaction unit, second solid-liquid separator and second dryer; The discharging opening of crushing and screening device is communicated with the charging aperture of first reaction unit; The discharging opening of first reaction unit is communicated with the charging aperture of first solid-liquid separator; The solid phase outlet of first solid-liquid separator is communicated with the charging aperture of rinsing machine; The liquid outlet of rinsing machine is communicated with liquid dispensing device, and the solid phase outlet of rinsing machine is communicated with the charging aperture of first dryer, and the discharging opening of first dryer is communicated with the charging aperture of screening dust arrester; The liquid phase outlet of first solid-liquid separator is communicated with the charging aperture of stating liquid dispensing device; The discharging opening of liquid dispensing device is communicated with the charging aperture of second reaction unit, and the discharging opening of second reaction unit is communicated with the charging aperture of second solid-liquid separator, and the solid phase outlet of second solid-liquid separator is communicated with the charging aperture of second dryer.
The present invention is with the system of producing sulfuric acid and jointly sulfonated coal and humic acid, and the alr mode of wherein said first reaction unit is that bubble type stirs, and the alr mode of second reaction unit also stirs for bubble type.
The present invention can be through input sulfuric acid and coal with the system of producing sulfuric acid and jointly sulfonated coal and humic acid, and coproduction sulfonated coal and humic acid when solving the acid-bearing wastewater discharging, have increased economic benefit.
Below in conjunction with accompanying drawing the present invention is described further.
Description of drawings
Fig. 1 is the structural representation of the present invention with the system of producing sulfuric acid and jointly sulfonated coal and humic acid.
The specific embodiment
As shown in Figure 1, the present invention comprises crushing and screening device 1, first reaction unit 2, first solid-liquid separator 3, rinsing machine 4, first dryer 5, screening dust arrester 6, liquid dispensing device 7, second reaction unit 8, second solid-liquid separator 9 and second dryer 10 with the system of producing sulfuric acid and jointly sulfonated coal and humic acid.The discharging opening of crushing and screening device 1 is communicated with the charging aperture of first reaction unit 2; The discharging opening of first reaction unit 2 is communicated with the charging aperture of first solid-liquid separator 3; The solid phase outlet of first solid-liquid separator 3 is communicated with the charging aperture of rinsing machine 4; The liquid outlet of rinsing machine 4 is communicated with liquid dispensing device 7, and the solid phase outlet of rinsing machine 4 is communicated with the charging aperture of first dryer 5, and the discharging opening of first dryer 5 is communicated with the charging aperture of screening dust arrester 6; The liquid phase outlet of first solid-liquid separator 3 is communicated with the charging aperture of liquid dispensing device 7; The discharging opening of liquid dispensing device 7 is communicated with the charging aperture of second reaction unit 8, and the discharging opening of second reaction unit 8 is communicated with the charging aperture of second solid-liquid separator 9, and the solid phase outlet of second solid-liquid separator 9 is communicated with the charging aperture of second dryer 10.
As shown in Figure 1, the present invention at first with adding brown coal in the crushing and screening device 1, certainly, also can add coals such as bituminous coal with the system of producing sulfuric acid and jointly sulfonated coal and humic acid in use, and selected coal should select for use intensity high, the coal that carbon content is higher relatively.Brown coal are behind crushing and screening device 1 crushing and screening; Obtain the brown coal particle of granularity, then the brown coal particle is put into first reaction unit 2, in first reaction unit 2, add concentration simultaneously more than or equal to 50% sulfuric acid less than 30mm; The mass ratio of sulfuric acid and brown coal particle is 2:1 ~ 6:1; Stir, keep 100 ~ 200 ℃ temperature conditions, reacted 4 ~ 20 hours.In the present embodiment, the concentration of the sulfuric acid that adds in first reaction unit 2 is 90% ~ 98%, and the mass ratio of sulfuric acid and brown coal particle is 3:1 ~ 5:1, under 150 ~ 175 ℃ temperature conditions, reacts 8 ~ 13 hours.First reaction unit 2 can adopt stirred autoclave.First reaction unit 2 also can adopt bubbling bed reactor; Its bottom feeds 100 ~ 300 ℃ industrial waste gas or resolves 100 ~ 300 ℃ the parsing hot-air that forms after the activated coke; Both can make full use of waste heat contained in the waste gas comes heat to the reaction of sulfuric acid in the bubbling bed reactor and brown coal particle to be provided; Can pass through bubbling again, sulfuric acid and brown coal particle are fully stirred, wherein the waste gas that feeds of first reaction unit, 2 bottoms or the temperature of resolving hot-air are preferred 180 ~ 240 ℃.The material that obtains after 2 reactions of first reaction unit is sent into first solid-liquid separator 3; The solid phase outlet of first solid-liquid separator 3 obtains containing the sulfonated coal of a small amount of sulfuric acid; It is fed in rinsing machine 4, incite somebody to action sulfuric acid flush away wherein through washing, the sulfonated coal that obtains is sent into first dryer 5; Sulfonated coal after the oven dry obtains finished product sulfonated coal particle after sending into the 6 screening dedustings of screening dust arrester.The liquid phase outlet of first solid-liquid separator 3 and the liquid outlet of rinsing machine 4 all are communicated with liquid dispensing device 7, and the sulfuric acid solution in the liquid dispensing device 7 is through adding the entry or the concentrated sulfuric acid, and making the concentration adjustment of the sulfuric acid solution in the liquid dispensing device 7 is 10% ~ 20%, and preferred 16% ~ 19%.The sulfuric acid solution that regulates is sent into second reaction unit 8 by liquid dispensing device 7; In second reaction unit 8, add humic acid content simultaneously more than or equal to 30% brown coal particle, certainly, the humic acid material coal also can be selected the coal that other wind degree of oxidation is high, humic acid content is high for use; The mass ratio of sulfuric acid solution and brown coal particle is 1:1 ~ 2:1; The two is stirred, under 40 ~ 80 ℃ temperature conditions, reacted 30 ~ 120 minutes.In the present embodiment, the mass ratio of sulfuric acid solution and brown coal particle is preferred 1:1 ~ 1.4:1 in second reaction unit 8, under 50 ~ 70 ℃ temperature conditions, reacts 40 ~ 60 minutes.Second reaction unit 8 can adopt stirred autoclave.Second reaction unit 8 also can adopt bubbling bed reactor; Its bottom feeds 50 ~ 120 ℃ useless flue gas; 70 ~ 100 ℃ useless flue gas behind the preferred dry brown coal adopts the mode that feeds useless flue gas, can make full use of waste heat contained in the waste gas and come heat to the reaction of sulfuric acid in the bubbling bed reactor and brown coal particle to be provided; Can pass through bubbling again, sulfuric acid and brown coal particle are fully stirred.The material that obtains after the reaction in second reaction unit 8 is sent into second solid-liquid separator 9; The liquid phase outlet of second solid-liquid separator 9 obtains liquid humic acid bullion 11; The solid that the solid phase outlet of second solid-liquid separator 9 obtains obtains solid-state humic acid bullion after sending into 10 oven dry of second dryer.
Embodiment 1:
Use the method for producing sulfuric acid and jointly sulfonated coal and humic acid to be:
1, be 50% sulfuric acid and granularity less than the brown coal particle of 30mm with concentration is that the ratio of 2:1 joins in first reaction unit, stirs, under 100 ℃ temperature conditions, reacted 4 hours according to mass ratio;
2, with equipment for separating liquid from solid with reacted separating substances, the solid that obtains is dried after washing, and obtains sulfonated coal;
3, the pickle of liquid that obtains after the Separation of Solid and Liquid and the formation of washing back is mixed; Adding water or sulfuric acid then, be adjusted to concentration and be 10% sulfuric acid solution, be 30% brown coal particle with the sulfuric acid solution that obtains and humic acid content according to mass ratio is that the ratio of 1:1 joins in second reaction unit; Stir; Under 40 ℃ temperature conditions, reacted 30 minutes, obtain the humic acid crude mixture.
Embodiment 2:
Use the method for producing sulfuric acid and jointly sulfonated coal and humic acid to be:
1, be 95% sulfuric acid and granularity less than the brown coal particle of 30mm with concentration is that the ratio of 6:1 joins in first reaction unit, stirs, under 200 ℃ temperature conditions, reacted 20 hours according to mass ratio;
2, with equipment for separating liquid from solid with reacted separating substances, the solid that obtains is dried after washing, and obtains sulfonated coal;
3, the pickle of liquid that obtains after the Separation of Solid and Liquid and the formation of washing back is mixed; Adding water or sulfuric acid then, be adjusted to concentration and be 20% sulfuric acid solution, be 55% brown coal particle with the sulfuric acid solution that obtains and humic acid content according to mass ratio is that the ratio of 2:1 joins in second reaction unit; Stir; Under 80 ℃ temperature conditions, reacted 120 minutes, obtain the humic acid crude mixture.
Embodiment 3:
Use the method for producing sulfuric acid and jointly sulfonated coal and humic acid to be:
1, be 95% sulfuric acid and granularity less than the brown coal particle of 30mm with concentration is that the ratio of 3:1 joins in first reaction unit, stirs, under 170 ℃ temperature conditions, reacted 15 hours according to mass ratio;
2, with equipment for separating liquid from solid with reacted separating substances, the solid that obtains is dried after washing, and obtains sulfonated coal;
3, the pickle of liquid that obtains after the Separation of Solid and Liquid and the formation of washing back is mixed; Adding water or sulfuric acid then, be adjusted to concentration and be 15% sulfuric acid solution, be 65% brown coal particle with the sulfuric acid solution that obtains and humic acid content according to mass ratio is that the ratio of 1.5:1 joins in second reaction unit; Stir; Under 70 ℃ temperature conditions, reacted 80 minutes, obtain the humic acid crude mixture.
Embodiment 4:
Use the method for producing sulfuric acid and jointly sulfonated coal and humic acid to be:
1, be 90% sulfuric acid and granularity less than the brown coal particle of 30mm with concentration is that the ratio of 3:1 joins in first reaction unit, stirs, under 150 ℃ temperature conditions, reacted 8 hours according to mass ratio;
2, with equipment for separating liquid from solid with reacted separating substances, the solid that obtains is dried after washing, and obtains sulfonated coal;
3, the pickle of liquid that obtains after the Separation of Solid and Liquid and the formation of washing back is mixed; Adding water or sulfuric acid then, be adjusted to concentration and be 16% sulfuric acid solution, be 70% brown coal particle with the sulfuric acid solution that obtains and humic acid content according to mass ratio is that the ratio of 1.2:1 joins in second reaction unit; Stir; Under 50 ℃ temperature conditions, reacted 30 ~ 120 minutes, obtain the humic acid crude mixture.
Embodiment 5:
Use the method for producing sulfuric acid and jointly sulfonated coal and humic acid to be:
1, being 80% sulfuric acid and granularity with concentration joins in first reaction unit less than the brown coal particle of the 30mm ratio according to mass ratio 5:1, stirs, and under 175 ℃ temperature conditions, reacts 13 hours;
2, with equipment for separating liquid from solid with reacted separating substances, the solid that obtains is dried after washing, and obtains sulfonated coal;
3, the pickle of liquid that obtains after the Separation of Solid and Liquid and the formation of washing back is mixed; Adding water or sulfuric acid then, be adjusted to concentration and be 19% sulfuric acid solution, be 65% brown coal particle with the sulfuric acid solution that obtains and humic acid content according to mass ratio is that the ratio of 1.4:1 joins in second reaction unit; Stir; Under 40 ℃ temperature conditions, reacted 60 minutes, obtain the humic acid crude mixture.
Embodiment 6:
Use the method for producing sulfuric acid and jointly sulfonated coal and humic acid to be:
1, be 98% sulfuric acid and granularity less than the brown coal particle of 30mm with concentration is that the ratio of 3.5:1 joins in first reaction unit, stirs, under 165 ℃ temperature conditions, reacted 11 hours according to mass ratio;
2, with equipment for separating liquid from solid with reacted separating substances, the solid that obtains is dried after washing, and obtains sulfonated coal;
3, the pickle of liquid that obtains after the Separation of Solid and Liquid and the formation of washing back is mixed; Adding water or sulfuric acid then, be adjusted to concentration and be 17% sulfuric acid solution, be 60% brown coal particle with the sulfuric acid solution that obtains and humic acid content according to mass ratio is that the ratio of 1.3:1 joins in second reaction unit; Stir; Under 61 ℃ temperature conditions, reacted 50 minutes, obtain the humic acid crude mixture.
The fertilizer that contains humic acid, in agricultural production, have improving the soil, promote fertilizer efficiency, stimulating growth, slightly through degeneration-resistant, improve quality five and act on greatly.The thing of humic acid quilt can sting kinase activity after absorbing, and promotes root system development, improves absorption function, and the synthetic and metabolism of vitamin, starch, amino acid, nucleic acid, protein etc. is played a role, thereby improves the general level of the health and the anti-adversity ability of plant.Can increase soil fertility indirectly, improve water and fertilizer condition or improve nutrient and effectively promote growth and development of plants through complexing solubilising property through improving soil property.The present invention at first utilizes the concentrated acid sulfonation coal particles, produces sulfonated coal, and the acid pickle after will washing then is used for oxidation humic acid material coal; Increase the content of the humic acid of 5 ~ 20% (mass percents) in the humic acid material coal; Therefore, the present invention utilizes acid-bearing wastewater to produce humic acid when producing sulfonated coal; Having solved the acid-bearing wastewater discharging, improved economic benefit of enterprises.
Above-described embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (10)
1. the method with producing sulfuric acid and jointly sulfonated coal and humic acid is characterized in that comprising the following steps:
A, the coal particles of granularity less than 30mm is provided;
B, be that the ratio of 2:1 ~ 6:1 joins in first reaction unit more than or equal to 50% sulfuric acid and the particle after the above-mentioned pulverizing according to mass ratio, stir, under 100 ~ 200 ℃ temperature conditions, reacted 4 ~ 20 hours concentration;
C, with first equipment for separating liquid from solid with reacted separating substances, the solid that obtains is dried after washing, and obtains sulfonated coal;
D, the pickle that the liquid that obtains after the Separation of Solid and Liquid and washing back are formed are mixed; Adding water or sulfuric acid then, be adjusted to concentration and be 10% ~ 20% sulfuric acid solution, is that the ratio of 1:1 ~ 2:1 join in second reaction unit more than or equal to 30% humic acid material coal particle according to mass ratio with the sulfuric acid solution that obtains and humic acid content; Stir; Under 40 ~ 80 ℃ temperature conditions, reacted 30 ~ 120 minutes, obtain the humic acid crude mixture.
2. the method with producing sulfuric acid and jointly sulfonated coal and humic acid according to claim 1 is characterized in that: the alr mode of the reactant in said step b and the steps d is that mechanical system stirs.
3. the method with producing sulfuric acid and jointly sulfonated coal and humic acid according to claim 1; It is characterized in that: the alr mode of the reactant among the said step b is that bubble type stirs, and feeds 100 ~ 300 ℃ waste gas in the bottom of reaction unit or activated coke is resolved 100 ~ 300 ℃ the parsing hot-air that the back forms.
4. the method with producing sulfuric acid and jointly sulfonated coal and humic acid according to claim 3 is characterized in that: among the said step b, waste gas that feeds in the bottom of reaction unit or the temperature of resolving hot-air are 180 ~ 240 ℃.
5. the method with producing sulfuric acid and jointly sulfonated coal and humic acid according to claim 1 is characterized in that: the alr mode of the reactant in the said steps d is that bubble type stirs, and feeds 50 ~ 120 ℃ useless flue gas in the bottom of reaction unit.
6. the method with producing sulfuric acid and jointly sulfonated coal and humic acid according to claim 5 is characterized in that: in the said steps d, and the useless flue gas after the useless flue gas that feeds in the bottom of reaction unit is dry brown coal, its temperature is 70 ~ 100 ℃.
7. the method with producing sulfuric acid and jointly sulfonated coal and humic acid according to claim 1 is characterized in that: among the said step b, the mass ratio of sulfuric acid and particle is 3:1 ~ 5:1, under 150 ~ 175 ℃ temperature conditions, reacts 8 ~ 13 hours.
8. the method with producing sulfuric acid and jointly sulfonated coal and humic acid according to claim 1; It is characterized in that: the concentration of the sulfuric acid that reacts in the said steps d is 16% ~ 19%; The mass ratio of sulfuric acid solution and coal particles is 1:1 ~ 1.4:1, under 50 ~ 70 ℃ temperature conditions, reacts 40 ~ 60 minutes.
9. system with producing sulfuric acid and jointly sulfonated coal and humic acid; It is characterized in that: comprise crushing and screening device (1), first reaction unit (2), first solid-liquid separator (3), rinsing machine (4), first dryer (5), screening dust arrester (6), liquid dispensing device (7), second reaction unit (8), second solid-liquid separator (9) and second dryer (10); The discharging opening of said crushing and screening device (1) is communicated with the charging aperture of first reaction unit (2); The discharging opening of first reaction unit (2) is communicated with the charging aperture of first solid-liquid separator (3); The solid phase outlet of said first solid-liquid separator (3) is communicated with the charging aperture of rinsing machine (4); The liquid outlet of said rinsing machine (4) is communicated with liquid dispensing device (7); The solid phase outlet of rinsing machine (4) is communicated with the charging aperture of first dryer (5); The discharging opening of first dryer (5) is communicated with the charging aperture of screening dust arrester (6); The liquid phase outlet of said first solid-liquid separator (3) is communicated with the charging aperture of said liquid dispensing device (7); The discharging opening of said liquid dispensing device (7) is communicated with the charging aperture of second reaction unit (8), and the discharging opening of second reaction unit (8) is communicated with the charging aperture of second solid-liquid separator (9), and the solid phase outlet of said second solid-liquid separator (9) is communicated with the charging aperture of second dryer (10).
10. the system with producing sulfuric acid and jointly sulfonated coal and humic acid according to claim 9 is characterized in that: the alr mode of said first reaction unit (2) is that bubble type stirs, and the alr mode of said second reaction unit (8) is that bubble type stirs.
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Cited By (4)
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| CN104353429A (en) * | 2014-11-05 | 2015-02-18 | 华玉叶 | Process for preparing sulfide coal |
| CN111233573A (en) * | 2020-01-19 | 2020-06-05 | 浙江丰瑜生态科技股份有限公司 | Newly-reclaimed rice field soil improvement humic acid compound fertilizer and preparation method thereof |
| CN111233550A (en) * | 2020-01-19 | 2020-06-05 | 浙江丰瑜生态科技股份有限公司 | Humic acid water-soluble fertilizer suitable for hickory planting and preparation method and application thereof |
| CN112661976A (en) * | 2020-12-21 | 2021-04-16 | 安徽工业大学 | Preparation method of low-rank coal-based high-efficiency water reducing agent |
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| CN202921325U (en) * | 2012-08-09 | 2013-05-08 | 北京康瑞新源净化技术有限公司 | System for coproduction of sulfonated coal and humic acid by using sulfuric acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104353429A (en) * | 2014-11-05 | 2015-02-18 | 华玉叶 | Process for preparing sulfide coal |
| CN111233573A (en) * | 2020-01-19 | 2020-06-05 | 浙江丰瑜生态科技股份有限公司 | Newly-reclaimed rice field soil improvement humic acid compound fertilizer and preparation method thereof |
| CN111233550A (en) * | 2020-01-19 | 2020-06-05 | 浙江丰瑜生态科技股份有限公司 | Humic acid water-soluble fertilizer suitable for hickory planting and preparation method and application thereof |
| CN111233550B (en) * | 2020-01-19 | 2021-11-23 | 浙江丰瑜生态科技股份有限公司 | Humic acid water-soluble fertilizer suitable for hickory planting and preparation method and application thereof |
| CN111233573B (en) * | 2020-01-19 | 2021-11-30 | 浙江丰瑜生态科技股份有限公司 | Newly-reclaimed rice field soil improvement humic acid compound fertilizer and preparation method thereof |
| CN112661976A (en) * | 2020-12-21 | 2021-04-16 | 安徽工业大学 | Preparation method of low-rank coal-based high-efficiency water reducing agent |
| CN112661976B (en) * | 2020-12-21 | 2022-07-12 | 安徽工业大学 | Preparation method of low-rank coal-based high-efficiency water reducing agent |
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| CN102773079B (en) | 2015-02-18 |
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