CN105498279A - Method for effectively increasing hot extraction yield of coal - Google Patents
Method for effectively increasing hot extraction yield of coal Download PDFInfo
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- CN105498279A CN105498279A CN201510979337.6A CN201510979337A CN105498279A CN 105498279 A CN105498279 A CN 105498279A CN 201510979337 A CN201510979337 A CN 201510979337A CN 105498279 A CN105498279 A CN 105498279A
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Abstract
The invention discloses a method for effectively increasing hot extraction yield of coal. Crushed and dried coal granules, a catalyst and a solvent are sufficiently mixed and added to a high-pressure reaction kettle, the mixture is heated under certain pressure to reach a set temperature after nitrogen gas replacement, black and bright hyperpure coal is obtained after hot extraction, filtering, washing and drying, and the catalyst is lewis acid metal salt or an acid ion liquid. The metal salt or acid ion liquid catalyst can be separated from a reaction system and repeatedly used, the hot extraction yield of the coal can be effectively increased by more than 20%-100%, the yield of hyperpure coal is 60%-85%, and the ash content of the hyperpure coal is smaller than 0.1%. The hot extraction rate of the coal is high, the quality is good, the production cost is low, and the method has wide market application prospect.
Description
Technical field
The present invention relates to a kind of method of effective raising coal extraction heat yield, specifically a kind of Lewis Acid metal salt or acidic ionic liquid catalysts prepare the application in super clean coal at hot extraction process, belong to chemical technology field.
Background technology
The solvent heat extraction of coal is the process utilizing organic solvent extraction coal under the high temperature conditions.Taken out by organic solvent extracting after organic macromolecule generation chain rupture and the chemical reaction such as to dissociate in coal under high temperature, inorganic mineral component to be then retained in residue thus to obtain super clean coal.The hot solvent extraction process of coal belongs to physics-chemical reaction, not only has important theory significance to its research, and has actual development and application values.(MiuraK, ShimadaM, the MaeK such as Miura, HuanH.Fuel, 2001,80 (11): 1573-1582) by finding the research of heterogeneity organic solvent, using polar solvent than using non-polar solven and can obtain higher extraction yield.(ZhangL, TakanohashiT, the SaitoI such as Zhang, etal.Fuel, 2008,87 (11): 2628-2640) investigated the impact of dissimilar acid on metal ion in coal and content of ashes, found that low-kappa number coal sample can improve the extraction heat rate of solvent.(the LiCQ such as Li, TakanohashiT, YoshidaT, etal.Energy & Fuels, 2004,18 (1): 97-101) have studied the impact of the process conditions such as extraction temperature and time on extraction yield, find the rising along with extraction temperature, extraction yield significantly increases.
The research that the domestic solvent heat about coal extracts is considerably less.China Coal Research Institute (Shi Zhijie, Zhang Shengzhen, Xing Lingyan etc. coal conversion, 2009,32 (1): 34-39) utilize coal liquefaction derived oils as the extraction heat solvent of coal, extraction heat device have studied the extraction heat performance of the low-order coal such as Datang Shengli Brown.The extraction heat rate of coal raises with temperature and obviously increases, and when being increased to 430 DEG C by 18.7% when 340 DEG C 59.5%, and the solid thermal extract rate of recovery reaches peak 32.4% 390 DEG C time.
All do not relate to the use of catalyst in the solvent heat abstraction technique of existing coal, therefore, how to select suitable catalyst and use it for coal solvent heat extraction, to improve the extraction heat yield of coal, be the key of dealing with problems.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of effective raising coal extraction heat yield, and it has catalyst and can reclaim and recycle, and coal extraction heat rate is high, super clean coal quality is good, and the advantages such as production cost is low, have wide market application foreground.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
The method of a kind of effective raising coal extraction heat yield of the present invention, it comprises the following steps:
A, coal dust is broken to Li Du≤200 μm, under 100 ~ 150 DEG C of conditions dry 12 ~ 48 hours for subsequent use.
B, the dried coal grain of Lewis Acid metal salt or acidic ion liquid, step a gained and solvent are fully mixed after add in autoclave, its quality proportioning is Lewis Acid metal salt or acidic ion liquid: dried coal grain: solvent=0.01 ~ 2:0.5 ~ 5:5 ~ 20, the best is: 1:4:20.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen to 0 ~ 5MPa, extraction temperature 300 ~ 450 DEG C, constant temperature, after 0.1 ~ 2 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.05 ~ 0.1 by volume, add distilled water, after abundant stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.
The method of above-mentioned a kind of effective raising coal extraction heat yield, can also comprise the following steps: e, when used catalyst is Lewis Acid metal salt, absolute ethyl alcohol is added in the aqueous phase of steps d gained, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separate out Lewis Acid metal salt catalyst, filter, the solvent that the recovery of the Lewis Acid metal salt catalyst leached and steps d gained obtains is recycled again.
F, the ethanol water after Lewis Acid metal salt catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle;
G, when used catalyst is acidic ion liquid, the aqueous phase of steps d gained is carried out decompression distillation, the solvent that the recovery of isolated acidic ionic liquid catalysts and steps d gained obtains recycles again.
Preferably, described coal is brown coal, bituminous coal or anthracite, especially to the high-order coal in bituminous coal and anthracite Be very effective.
Preferably, described Louis's slaine is one or more of ferric sulfate, zinc sulfate, magnesium sulfate, iron chloride, zinc chloride, magnesium chloride, ferric nitrate, zinc nitrate or magnesium nitrate; Described acidic ion liquid be cation with sulfonic group structure, anion is bisulfate ion.
Described solvent is the organic solvent containing aromatic ring structure, preferably technical grade GB washing oil, 1-methyl naphthalene, 2-methyl naphthalene or 1-METHYLPYRROLIDONE etc.
The beneficial effect that the present invention compared with prior art has is:
(1) coal of the present invention effectively can improve coal extraction heat rate and reaches more than 20%-100%, and super clean coal yield is 60%-85%, and ultrapure pit ash is less than 0.1%.
(2) method of a kind of effective raising coal extraction heat yield of the present invention, the Lewis Acid metal salt used or acidic ionic liquid catalysts can be separated and reuse from reaction system.
(3) coal extraction heat rate of the present invention is high, super clean coal quality is good, and production cost is low, and extractant is recyclable recycles, and has wide market application foreground.Detailed in Example.
Detailed description of the invention
The present invention is described in further detail below.
Embodiment 1
A, brown coal powder is broken to Li Du≤200 μm, under 100 DEG C of conditions dry 48 hours for subsequent use.
B, by the moisture-free coal grain 50g of 1g ferric sulfate and step a gained, add technical grade GB washing oil 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 5MPa, be rapidly heated to 300 DEG C under rotating speed is 600 turns/min stirring, constant temperature, after 2 hours, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.05 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 81.2%, and super clean coal yield is 72.8%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out ferric sulfate catalyst, filters, and is again recycled by the solvent that the recovery of the ferric sulfate catalyst leached and steps d gained obtains.
F, the ethanol water after ferric sulfate catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 2
A, bituminous coal powder is broken to Li Du≤200 μm, under 150 DEG C of conditions dry 12 hours for subsequent use.
B, by the moisture-free coal grain 125g of 50g zinc sulfate and step a gained, add 1-methyl naphthalene 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 0MPa, be rapidly heated to 450 DEG C under rotating speed is 100 turns/min stirring, constant temperature, after 0.1 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.1 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 88.2%, and super clean coal yield is 80.8%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out zinc sulfate catalyst, filters, and is again recycled by the solvent that the recovery of the zinc sulfate catalyst leached and steps d gained obtains.
F, the ethanol water after zinc sulfate catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 3
A, bituminous coal powder is broken to Li Du≤200 μm, under 110 DEG C of conditions dry 24 hours for subsequent use.
B, by the moisture-free coal grain 100g of 25g magnesium sulfate and step a gained, add 2-methyl naphthalene 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 2MPa, be rapidly heated to 400 DEG C under rotating speed is 300 turns/min stirring, constant temperature, after 0.5 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.05 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 90.3%, and super clean coal yield is 85%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out magnesium sulfate catalyst, filters, and is again recycled by the solvent that the recovery of the magnesium sulfate catalyst leached and steps d gained obtains.
F, the ethanol water after magnesium sulfate catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 4
A, bituminous coal powder is broken to Li Du≤200 μm, under 130 DEG C of conditions dry 32 hours for subsequent use.
B, by the moisture-free coal grain 80g of 10g iron chloride and step a gained, add 1-METHYLPYRROLIDONE 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 1MPa, be rapidly heated to 380 DEG C under rotating speed is 400 turns/min stirring, constant temperature, after 1 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.07 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 77.3%, and super clean coal yield is 74.2%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out ferric chloride catalyst, filters, and is again recycled by the solvent that the recovery of the ferric chloride catalyst leached and steps d gained obtains.
F, the ethanol water after ferric chloride catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 5
A, anchracite duff is broken to Li Du≤200 μm, under 105 DEG C of conditions dry 32 hours for subsequent use.
B, by the moisture-free coal grain 110g of 20g zinc chloride and step a gained, add 2-methyl naphthalene 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 4MPa, be rapidly heated to 350 DEG C under rotating speed is 500 turns/min stirring, constant temperature, after 0.7 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.06 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 68.3%, and super clean coal yield is 60%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out zinc chloride catalyst, filters, and is again recycled by the solvent that the recovery of the zinc chloride catalyst leached and steps d gained obtains.
F, the ethanol water after zinc chloride catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 6
A, bituminous coal powder is broken to Li Du≤200 μm, under 145 DEG C of conditions dry 15 hours for subsequent use.
B, by the moisture-free coal grain 90g of 30g magnesium chloride and step a gained, add 1-methyl naphthalene 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 1MPa, be rapidly heated to 330 DEG C under rotating speed is 200 turns/min stirring, constant temperature, after 1.7 hours, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.03 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 80.3%, and super clean coal yield is 75%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out magnesium chloride catalyst, filters, and is again recycled by the solvent that the recovery of the magnesium chloride catalyst leached and steps d gained obtains.
F, the ethanol water after magnesium chloride catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 7
A, brown coal powder is broken to Li Du≤200 μm, under 130 DEG C of conditions dry 48 hours for subsequent use.
B, by the moisture-free coal grain 70g of 5g ferric nitrate and step a gained, add technical grade GB washing oil 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 2MPa, be rapidly heated to 350 DEG C under rotating speed is 400 turns/min stirring, constant temperature, after 1.5 hours, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.02 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 83.4%, and super clean coal yield is 73.8%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out ferric nitrate catalyst, filters, and is again recycled by the solvent that the recovery of the ferric nitrate catalyst leached and steps d gained obtains.
F, the ethanol water after ferric nitrate catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 8
A, bituminous coal powder is broken to Li Du≤200 μm, under 110 DEG C of conditions dry 48 hours for subsequent use.
B, by the moisture-free coal grain 60g of 3g zinc nitrate and step a gained, add technical grade GB washing oil 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 1MPa, be rapidly heated to 380 DEG C under rotating speed is 400 turns/min stirring, constant temperature, after 1.2 hours, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.04 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 85.4%, and super clean coal yield is 74.8%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out zinc nitrate catalyst, filters, and is again recycled by the solvent that the recovery of the zinc nitrate catalyst leached and steps d gained obtains.
F, the ethanol water after zinc nitrate catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 9
A, bituminous coal powder is broken to Li Du≤200 μm, under 110 DEG C of conditions dry 48 hours for subsequent use.
B, by the moisture-free coal grain 60g of 3g magnesium nitrate and step a gained, add 1-methyl naphthalene 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 3MPa, be rapidly heated to 370 DEG C under rotating speed is 300 turns/min stirring, constant temperature, after 1.1 hours, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.06 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 82.4%, and super clean coal yield is 73.8%, and ash content is less than 0.1%.
E, in the aqueous phase of steps d gained, add absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separates out magnesium nitrate catalyst, filters, and is again recycled by the solvent that the recovery of the magnesium nitrate catalyst leached and steps d gained obtains.
F, the ethanol water after magnesium nitrate catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
Embodiment 10
A, brown coal powder is broken to Li Du≤200 μm, under 130 DEG C of conditions dry 48 hours for subsequent use.
B, by 40gN, N, N-trimethyl-N-sulphur butyl ammonium hydrogen sulfate ([HSO
3-b-N (CH
3)
3] HSO
4) the moisture-free coal grain 100g of acidic ion liquid and step a gained, add technical grade GB washing oil 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 2MPa, be rapidly heated to 380 DEG C under rotating speed is 400 turns/min stirring, constant temperature, after 1 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.1 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 79.4%, and super clean coal yield is 75.8%, and ash content is less than 0.1%.
E, the aqueous phase of steps d gained is carried out decompression distillation, isolated N, N, N-trimethyl-N-sulphur butyl ammonium hydrogen sulfate ([HSO
3-b-N (CH
3)
3] HSO
4) solvent that the recovery of acidic ionic liquid catalysts and steps d gained obtains recycles again.
Embodiment 11
A, bituminous coal powder is broken to Li Du≤200 μm, under 100 DEG C of conditions dry 72 hours for subsequent use.
B, by 30g1-vinyl-3-sulfobutyl imidazole bisulfate ([HSO
3-bvim] HSO
4) the moisture-free coal grain 70g of acidic ion liquid and step a gained, add 1-methyl naphthalene 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 0MPa, be rapidly heated to 360 DEG C under rotating speed is 300 turns/min stirring, constant temperature, after 0.5 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.08 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 89.4%, and super clean coal yield is 84.5%, and ash content is less than 0.1%.
E, the aqueous phase of steps d gained is carried out decompression distillation, isolated 1-vinyl-3-sulfobutyl imidazole bisulfate ([HSO
3-bvim] HSO
4) solvent that the recovery of acidic ionic liquid catalysts and steps d gained obtains recycles again.
Embodiment 12
A, anchracite duff is broken to Li Du≤200 μm, under 120 DEG C of conditions dry 48 hours for subsequent use.
B, by 50g1-sulphur butyl-3-methylimidazolium hydrogen sulphate salt ([HSO
3-bmim] HSO
4) the moisture-free coal grain 100g of acidic ion liquid and step a gained, add 2-methyl naphthalene 500g, after it is fully mixed, add in 1L autoclave.
C, in above-mentioned autoclave, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 2MPa, be rapidly heated to 350 DEG C under rotating speed is 500 turns/min stirring, constant temperature, after 0.7 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.1 by volume, add distilled water, after fully stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.The extraction heat rate of coal is 72.5%, and super clean coal yield is 68.8%, and ash content is less than 0.1%.
E, the aqueous phase of steps d gained is carried out decompression distillation, isolated 1-sulphur butyl-3-methylimidazolium hydrogen sulphate salt ([HSO
3-bmim] HSO
4) solvent that the recovery of acidic ionic liquid catalysts and steps d gained obtains recycles again.
The acidic ionic liquid catalysts used in above-described embodiment, can be prepared by existing known technology.
Claims (10)
1. effectively improve a method for coal extraction heat yield, it is characterized in that: make catalyst with slaine or acidic ion liquid, it comprises the following steps:
A, coal dust is broken to Li Du≤200 μm, under 100 ~ 150 DEG C of conditions dry 12 ~ 48 hours for subsequent use;
B, the dried coal grain of Lewis Acid metal salt or acidic ion liquid, step a gained and solvent are fully mixed after add in autoclave, its quality proportioning is Lewis Acid metal salt or acidic ion liquid: dried coal grain: solvent=0.01 ~ 2:0.5 ~ 5:5 ~ 20;
C, in the autoclave of step b, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen to 0 ~ 5MPa, extraction temperature 300 ~ 450 DEG C, constant temperature, after 0.1 ~ 2 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid;
D, by the amalgamation liquid of step c gained, amalgamation liquid and distilled water are 1:0.05 ~ 0.1 by volume, add distilled water, after abundant stirring, carry out Liquid liquid Separation, by oil phase wherein, carry out decompression distillation and obtain solid super clean coal, reclaim the solvent obtained and recycle.
2. the method for a kind of effective raising coal extraction heat yield as claimed in claim 1, characterized by further comprising following steps:
E, when used catalyst is Lewis Acid metal salt, absolute ethyl alcohol is added in the aqueous phase of steps d gained, the volume ratio of absolute ethyl alcohol and aqueous phase is 3:1, separate out Lewis Acid metal salt catalyst, filter, the solvent that the recovery of the Lewis Acid metal salt catalyst leached and steps d gained obtains is recycled again;
F, the ethanol water after Lewis Acid metal salt catalyst that removes of step e gained is carried out decompression distillation, isolate absolute ethyl alcohol and recycle.
3. the method for a kind of effective raising coal extraction heat yield as claimed in claim 1, characterized by further comprising following steps:
G, when used catalyst is acidic ion liquid, the aqueous phase of steps d gained is carried out decompression distillation, the solvent that the recovery of isolated acidic ionic liquid catalysts and steps d gained obtains recycles again.
4. the method for a kind of effective raising coal extraction heat yield as claimed in claim 1, is characterized in that:
In described step b, by quality proportioning, Lewis Acid metal salt or acidic ion liquid: dried coal grain: solvent=1:4:20.
5. the method for a kind of effective raising coal extraction heat yield as claimed in claim 1, is characterized in that:
Described step c is: in the autoclave of step b, with nitrogen displacement autoclave air wherein and inflated with nitrogen to 5MPa, keep pressure in still constant in 30min, then bleed off nitrogen, then inflated with nitrogen is to 2MPa, extraction temperature 400 DEG C, constant temperature, after 0.5 hour, obtains filtrate and filter residue after being filtered by reactant, by filter residue with after the solvent wash same with extraction phase, again washing lotion and filtrate are merged, obtain amalgamation liquid.
6. the method for a kind of effective raising coal extraction heat yield as claimed in claim 1, is characterized in that:
Described coal is brown coal, bituminous coal or anthracite.
7. the method for a kind of effective raising coal extraction heat yield as claimed in claim 1, is characterized in that: described Louis's slaine is one or more in ferric sulfate, zinc sulfate, magnesium sulfate, iron chloride, zinc chloride, magnesium chloride, ferric nitrate, zinc nitrate or magnesium nitrate.
8. the method for a kind of effective raising coal extraction heat yield as claimed in claim 1, is characterized in that: described acidic ion liquid be cation with sulfonic group structure, anion is bisulfate ion.
9. the method for a kind of effective raising coal extraction heat yield as claimed in claim 1, is characterized in that: described solvent is the organic solvent containing aromatic ring structure.
10. the method for a kind of effective raising coal extraction heat yield as claimed in claim 9, is characterized in that: described solvent is technical grade GB washing oil, 1-methyl naphthalene, 2-methyl naphthalene or 1-METHYLPYRROLIDONE.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865311A (en) * | 2018-06-01 | 2018-11-23 | 北京科技大学 | A kind of method that biomass/low-order coal prepares solid fuel |
| CN117866682A (en) * | 2024-02-05 | 2024-04-12 | 中南大学 | Method for preparing ultralow ash coal by taking coal as raw material through extraction |
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| JPS57115492A (en) * | 1981-01-07 | 1982-07-17 | Hitachi Ltd | Deashing method of coal |
| CN102512846A (en) * | 2011-11-22 | 2012-06-27 | 河北钢铁集团有限公司 | Method for thermally extracting coal |
| CN102733008A (en) * | 2012-06-21 | 2012-10-17 | 中国科学院过程工程研究所 | Method of preparing carbon fiber by using coal to directly liquefy residue-based asphalt vinyl material |
| CN103555357A (en) * | 2013-11-04 | 2014-02-05 | 华东理工大学 | Method for liquifying coal mildly |
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- 2015-12-23 CN CN201510979337.6A patent/CN105498279B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57115492A (en) * | 1981-01-07 | 1982-07-17 | Hitachi Ltd | Deashing method of coal |
| CN102512846A (en) * | 2011-11-22 | 2012-06-27 | 河北钢铁集团有限公司 | Method for thermally extracting coal |
| CN102733008A (en) * | 2012-06-21 | 2012-10-17 | 中国科学院过程工程研究所 | Method of preparing carbon fiber by using coal to directly liquefy residue-based asphalt vinyl material |
| CN103555357A (en) * | 2013-11-04 | 2014-02-05 | 华东理工大学 | Method for liquifying coal mildly |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108865311A (en) * | 2018-06-01 | 2018-11-23 | 北京科技大学 | A kind of method that biomass/low-order coal prepares solid fuel |
| CN117866682A (en) * | 2024-02-05 | 2024-04-12 | 中南大学 | Method for preparing ultralow ash coal by taking coal as raw material through extraction |
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| CN105498279B (en) | 2017-06-30 |
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