CN104449916A - Method for preparing high-concentration coal-water slurry from lignite through medium-temperature upgrading - Google Patents
Method for preparing high-concentration coal-water slurry from lignite through medium-temperature upgrading Download PDFInfo
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Abstract
The invention relates to a method for preparing high-concentration coal-water slurry from lignite through medium-temperature upgrading. The method is used for solving the problem of the existing low-rank coal that the slurry concentration is low. The method comprises the processes of carrying out deep drying on lignite, carrying out medium-temperature reaction, cooling upgraded coal and grinding the coal to produce slurry, wherein the deep drying and medium-temperature pyrolysis reaction are combined, so as to upgrade the lignite. According to the method, the process is simple, the production cost is low, and the prepared coal-water slurry is high in concentration and excellent in various properties, so that the utilization way of the low-rank coal, particularly the lignite, is expanded; the method is applicable to the preparation of the coal-water slurry for gasification.
Description
Technical field
The present invention relates to a kind of Coal Chemical Industry process for upgrading, in a kind of brown coal, high-concentration coal-water slurry method is prepared in warm upgrading specifically.
Background technology
In China, account for more than 55% of coal resources total amount with brown coal and the lower-grade metamorphic bituminous low-rank coal reserves for representative.Wherein, brown coal account for 13%, are mainly distributed in east Inner Mongolia and Yunnan, are distributed in the areas such as Heilungkiang, Liaoning, Shandong, Jilin and Guangxi on a small quantity; The lower-grade metamorphic bituminous areas such as being mainly distributed in Shaanxi, West Inner Mongolia and Xinjiang that is mainly distributed in.
Along with the high coal that goes bad is used fewer and fewer, the high-efficiency cleaning of low-rank coal utilizes and shows important day.Present stage, the Efficient Conversion Land use systems of low-rank coal was carry out pyrolysis after drying.End 2013, low-rank coal upgrading technology is more than 20 kinds, and wherein 13 kinds of pyrolytic techniques are in construction, trial run stage, and the extensive efficiency utilization of low order improving quality of coal by pyrolysis solid phase prod is the large problem that people face.
Low-rank coal reactive behavior is high, high as gasified raw material gasification efficiency.But coal rank are lower, inherent moisture is higher, carbon ratio is higher, the sludge forming performance of coal is poorer, is difficult to make high-concentration coal-water slurry.For coal water slurry gasification, water coal slurry concentration and quality higher, synthesis system production capacity increases, and than oxygen consumption and lower than coal consumption, after water coal slurry concentration improves, the economic benefit brought is very considerable.
For a long time, low-rank coal (particularly brown coal) prepares achieving no breakthrough property of high-concentration coal-water slurry technology progress, and the concentration of the direct levigate rear preparation coal water slurry of brown coal, cannot as boiler oil and coal gasifier raw material at 45%-50%.Exploitation low-rank coal prepares high-concentration coal-water slurry technology, can widen the utilization ways of coal resources in China.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, providing warm upgrading in the brown coal that a kind of technique is simple, energy-saving and cost-reducing, slurry concentration is high, be applicable to low-rank coal to prepare high-concentration coal-water slurry method.
Technical scheme comprises the following steps:
1) depth drying: granularity is less than or equal to 10mm brown coal and adds upgrading furnace, be less than 4% to brown coal drying to water content under normal pressure and inert gas environment, deviates from the gas of moisture in brown coal and absorption;
2) temperature reaction in: in being carried out under normal pressure and inert gas environment by the brown coal after depth drying, temperature is obtained by reacting upgraded coal, and described temperature of reaction controls at 600 DEG C-750 DEG C, and the residence time controls at 20-30min;
3) upgraded coal cooling: upgraded coal is quickly cooled to less than 60 DEG C under isolated air ambient;
4) coal-grinding slurrying: by levigate for cooled upgraded coal to the preparation coal water slurry that adds water after being less than 1mm.
In described step (1), the temperature of described depth drying controls at 150 DEG C-300 DEG C, and the residence time controls at 30-40min.
Temperature rise rate in described step (1) and (2) is 100-150.
In described step (4), the upgraded coal being less than 1mm then added water after stirring and prepare coal water slurry, mixing speed is for being 1000r/min, and churning time controls at 15-20min.
In described step (4), by levigate for cooled upgraded coal to add water after being less than 1mm preparation coal water slurry time, add with xylogen is the slurries additive agent of main raw material simultaneously.
The consumption of described slurries additive agent is 0.3% of upgraded coal quality.
Contriver conducts in-depth research the process that existing brown coal prepare coal water slurry, and ature of coal has great effect to water coal slurry concentration and mobility.There is significant limitation in low-rank coal (particularly brown coal) directly preparation coal water slurry, by first depth drying again in two step upgrading methods of warm solution can improve physical properties and the chemical property of coal.Slight chemical reaction is there is in depth drying while realization dehydration, degassed physical change, reach decarboxylation, depth drying significantly can also reduce brown coal moisture and oxygen-containing functional group content, strengthens the hydrophobicity on coal surface and improves the concentration being adsorbed on coal surface additive.On the basis of depth drying, in warm solution can reduce oxygen-containing functional group content in brown coal further, remove too much volatile matter, semicoke decomposes simultaneously, and volumetric shrinkage, improves the pore characteristic of coal, reach the effect carrying high-rank coals, improve the grindability index of brown coal, thus improve slurrying concentration.And if not drying and directly in warm solution, the large quantity of moisture contained in brown coal in pyrolytic process with brown coal generation chemical reaction, change the pore characteristic of semicoke and reduce its quality, pulping deleterious.In limiting in the present invention, warm pyrolysis temperature is 600 DEG C-750 DEG C, is more preferably 600 DEG C-700 DEG C, the too high quality that can reduce byproduct tar, in residence time of warm solution control at 20-30min, the long energy consumption that causes increases, too shortly causes reaction incomplete.
Further, temperature rise rate on depth drying and in the impact of warm solution preocess significantly.During fast pyrogenation, first thermal decomposition product is short for duration of contact with the coal grain of heat, can reduce the probability that semicoke carries out secondary reaction, but temperature rise rate also can not be too fast, the requirement of too fast temperature rise rate to equipment and material is harsh, and therefore, considered critical temperature rise rate is 100-150 DEG C/s.
Particle diameter is another factor water coal slurry concentration and mobility being had to great effect except ature of coal and additive.Brown coal are after artificial upgrading, and physical properties presents wide variation, and the granularity of upgraded coal can form good grain size distribution being less than within the scope of 1mm, effectively can improve slurry concentration.
Due to brown coal through depth drying and in warm solution, slurry performance effectively improves, and the xylogen that therefore only need add minute quantity just can improve the concentration of coal water slurry further.
Beneficial effect:
Present invention process is simple, and production cost is low, and the water coal slurry concentration of preparation is high, properties is excellent, has expanded the utilization ways of low-rank coal particularly brown coal, has been applicable to preparation gasification coal water slurry.
Embodiment
Embodiment 1, brown coal are crushed to below 10mm in advance, in gauge pressure is 0-0.1MPa and inert gas environment, drying temperature controls at 150 DEG C, temperature rise rate is at 100-150 DEG C/s, the residence time controls at 40min, and dried coal is warm solution in carrying out, and temperature of reaction controls at 750 DEG C, temperature rise rate is at 100-500 DEG C/s, and the residence time controls at 20min.Cooled upgraded coal uses ball mill to carry out coal-grinding sample preparation, and the diameter proportioning of steel ball is 20mm, 12mm and 5mm, and quality proportioning is 20%:50%:30%, and drum's speed of rotation is set in 170r/min, coal-grinding time 3min.Coal sample uses 1mm sieve to sieve, and be less than 1mm coal sample and add water and mix, the agitator re-using rotating speed 1000r/min stirs 18min, is finally prepared into embodiment coal water slurry sample.The results are shown in Table 3.
Embodiment 2, brown coal are crushed to below 10mm in advance, in normal pressure and inert gas environment, drying temperature controls at 280 DEG C of temperature rise rates at 100-150 DEG C/s, the residence time controls at 35min, dried coal is warm solution in carrying out, temperature of reaction controls at 620 DEG C, and temperature rise rate is at 100-500 DEG C/s, and the residence time controls at 25min.Cooled upgraded coal uses ball mill to carry out coal-grinding sample preparation, and the diameter proportioning of steel ball is 20mm, 12mm and 5mm, and quality proportioning is 20%:50%:30%, and drum's speed of rotation is set in 170r/min, coal-grinding time 3min.Coal sample uses 1mm sieve to sieve, be less than 1mm coal sample add water and additive (xylogen, consumption is 0.3%, wt of upgraded coal) and mix, the agitator re-using rotating speed 1000r/min stirs 15min, is finally prepared into embodiment coal water slurry sample.The results are shown in Table 3.
Embodiment 3, brown coal are crushed to below 10mm in advance, in normal pressure and inert gas environment, drying temperature controls at 300 DEG C of temperature rise rates at 100-150 DEG C/s, the residence time controls at 30min, dried coal is warm solution in carrying out, temperature of reaction controls at 600 DEG C, and temperature rise rate is at 100-500 DEG C/s, and the residence time controls at 30min.Cooled upgraded coal uses ball mill to carry out coal-grinding sample preparation, and the diameter proportioning of steel ball is 20mm, 12mm and 5mm, and quality proportioning is 20%:50%:30%, and drum's speed of rotation is set in 170r/min, coal-grinding time 3min.Coal sample uses 1mm sieve to sieve, be less than 1mm coal sample and add water and additive (ZM-19 High-efficient Water slurry additive, the Central-South Chemical Co., Ltd. in Changzhou produces, take xylogen as main raw material, consumption is 0.3% of upgraded coal, wt) and mix, the agitator re-using rotating speed 1000r/min stirs 20min, is finally prepared into embodiment coal water slurry sample.The results are shown in Table 3
Comparative example:
Comparative example 1, brown coal are crushed to below 10mm in advance, then coal sample are laid in equably in pallet, and the constant temperature blast drying oven putting into 105 DEG C carries out drying, time of drying 8h, to deviate from moisture in coal.Dried coal sample uses ball mill to carry out coal-grinding sample preparation, and drum's speed of rotation is set in 170r/min, coal-grinding time 3min.Take coal sample, then add water and mix, re-use high speed electric agitator and stir 20min, be finally prepared into comparative example coal water slurry sample.The results are shown in Table 3.
Comparative example 2, brown coal are crushed to below 10mm in advance, and in gauge pressure is 0-0.1MPa and inert gas environment, drying temperature controls at 280 DEG C, and temperature rise rate is at 100-150 DEG C/s, and the residence time controls at 30min.Cooled upgraded coal uses ball mill to carry out coal-grinding sample preparation, and the diameter proportioning of steel ball is 20mm, 12mm and 5mm, and quality proportioning is 20%:50%:30%, and drum's speed of rotation is set in 170r/min, coal-grinding time 3min.Coal sample uses 1mm sieve to sieve, be less than 1mm coal sample and add water and additive (ZM-19 High-efficient Water slurry additive, the Central-South Chemical Co., Ltd. in Changzhou produces, take xylogen as main raw material, consumption is 0.3% of upgraded coal, wt) and mix, the agitator re-using rotating speed 1000r/min stirs 20min, is finally prepared into embodiment coal water slurry sample.The results are shown in Table 3.
Comparative example 3, brown coal are crushed to below 10mm in advance, and in gauge pressure is 0-0.1MPa and inert gas environment, carry out low temperature pyrogenation, temperature of reaction controls at 620 DEG C, and temperature rise rate is at 100-150 DEG C/s, and the residence time controls at 30min.Cooled upgraded coal uses ball mill to carry out coal-grinding sample preparation, and the diameter proportioning of steel ball is 20mm, 12mm and 5mm, and quality proportioning is 20%:50%:30%, and drum's speed of rotation is set in 170r/min, coal-grinding time 3min.Coal sample uses 1mm sieve to sieve, be less than 1mm coal sample and add water and additive (ZM-19 High-efficient Water slurry additive, the Central-South Chemical Co., Ltd. in Changzhou produces, take xylogen as main raw material, consumption is 0.3% of upgraded coal, wt) and mix, the agitator re-using rotating speed 1000r/min stirs 20min, is finally prepared into embodiment coal water slurry sample.The results are shown in Table 3.
Described in the embodiment of the present invention and comparative example, brown coal select Inner Mongol brown coal, and coal index is in table 1 and table 2.
The brown coal ultimate analysis of table 1 Inner Mongol and technical analysis (wt, %)
Table 2 Inner Mongol brown coal HGI and grey melt temperature
The slurry performance of table 3 comparative example and embodiment coal water slurry sample
Remarks:
1. liquidity analysis adopt appearance method, be divided into excellent, good, in, differ from four grades.Excellent: smooth flow, uninterruptedly, good: to flow not smooth, have interruption, in: can not independently toward dirty, need by external force, poor: clustering phenomena is serious.
2. stability analysis adopt rod insert observation, coal water slurry sample is left standstill more than 12h and analyzes, be divided into excellent, good, in, differ from four grades.Excellent: without bleed, without precipitation, good: slight bleed, precipitate a little, in: precipitation is serious, poor: caking.
Brown coal through first depth drying again in the obtained upgraded coal pulping of two step upgrading methods of warm solution comparatively its performance of the direct pulping of brown coal be increased dramatically.Pyrolysis temperature is that 620 DEG C of upgraded coal best slurry concentrations present good mobility and stability at 67% (wt).The indexs such as the concentration in analytical table 3, viscosity, mobility and stability, the slurry concentration of the upgraded coal that the embodiment of the present invention obtains all is significantly increased and good stability compared to the slurry concentration of comparative example brown coal.
Claims (6)
1. in brown coal, a high-concentration coal-water slurry method is prepared in warm upgrading, it is characterized in that, comprises the following steps:
1) depth drying: granularity is less than or equal to 10mm brown coal and adds upgrading furnace, be less than 4% to brown coal drying to water content under normal pressure and inert gas environment, deviates from the gas of moisture in brown coal and absorption;
2) temperature reaction in: in being carried out under normal pressure and inert gas environment by the brown coal after depth drying, temperature is obtained by reacting upgraded coal, and described temperature of reaction controls at 600 DEG C-750 DEG C, and the residence time controls at 20-30min;
3) upgraded coal cooling: upgraded coal is quickly cooled to less than 60 DEG C under isolated air ambient;
4) coal-grinding slurrying: by levigate for cooled upgraded coal to the preparation coal water slurry that adds water after being less than 1mm.
2. in brown coal as claimed in claim 1, high-concentration coal-water slurry method is prepared in warm upgrading, and it is characterized in that, in described step (1), the temperature of described depth drying controls at 150 DEG C-300 DEG C, and the residence time controls at 30-40min.
3. in brown coal as claimed in claim 1, high-concentration coal-water slurry method is prepared in warm upgrading, it is characterized in that, the temperature rise rate in described step (1) and (2) is 100-150 DEG C/s.
4. in brown coal as claimed in claim 1, high-concentration coal-water slurry method is prepared in warm upgrading, it is characterized in that, in described step (4), then the upgraded coal being less than 1mm is added water after stirring and prepare coal water slurry, mixing speed is for being 1000r/min, and churning time controls at 15-20min.
5. in the brown coal as described in claim 1 or 4, high-concentration coal-water slurry method is prepared in warm upgrading, it is characterized in that, in described step (4), by levigate for cooled upgraded coal to add water after being less than 1mm preparation coal water slurry time, add with xylogen is the slurries additive agent of main raw material simultaneously.
6. in brown coal as claimed in claim 5, high-concentration coal-water slurry method is prepared in warm upgrading, and it is characterized in that, in described step (4), the consumption of described slurries additive agent is 0.3% of upgraded coal quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109628177A (en) * | 2019-01-22 | 2019-04-16 | 苏州永峰联环保科技有限公司 | A kind of ternary or polynary slurries additive agent |
| CN111575061A (en) * | 2020-05-29 | 2020-08-25 | 新奥科技发展有限公司 | Coal gasification system and coal water slurry concentration method |
| CN111944545A (en) * | 2020-07-23 | 2020-11-17 | 青岛华表新材料科技有限公司 | Process for integrally preparing formed coke by molding, drying and dry distilling pulverized coal |
| CN113403117A (en) * | 2020-03-17 | 2021-09-17 | 国家能源投资集团有限责任公司 | Gasified coal water slurry and preparation method and application thereof |
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| CN111944545A (en) * | 2020-07-23 | 2020-11-17 | 青岛华表新材料科技有限公司 | Process for integrally preparing formed coke by molding, drying and dry distilling pulverized coal |
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