CN112587957A - Liquid-liquid extraction and micro-solid-liquid extraction method for low-rank coal - Google Patents
Liquid-liquid extraction and micro-solid-liquid extraction method for low-rank coal Download PDFInfo
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- CN112587957A CN112587957A CN202011393574.1A CN202011393574A CN112587957A CN 112587957 A CN112587957 A CN 112587957A CN 202011393574 A CN202011393574 A CN 202011393574A CN 112587957 A CN112587957 A CN 112587957A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0261—Solvent extraction of solids comprising vibrating mechanisms, e.g. mechanical, acoustical
- B01D11/0265—Applying ultrasound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
Abstract
A liquid-liquid extraction and micro-solid-liquid extraction method of low-rank coal comprises the following steps: s1, breaking a coal sample, S2, carrying out hydrolysis by using water and alkali, S3, filtering, S4, carrying out liquid-liquid extraction, and S5, carrying out micro-solid-liquid extraction. According to the invention, coal particle hydro-alkali is firstly depolymerized into liquid or tiny solid clusters, and then the extraction is carried out by using an organic solvent, so that the extraction mechanism can be changed, the extraction process is accelerated, the extraction time is effectively shortened, the extract can be extracted more thoroughly, and the extraction efficiency is improved.
Description
Technical Field
The invention provides an extraction method of low-rank coal hydrolysis liquid, and belongs to the field of coal refining processing.
Background
China has abundant low-rank coal resources, and generally has the characteristics of high ash content, high moisture content and low calorific value. In fact, the coal is not only an energy source, but also a precious resource, and is an important raw material for preparing high value-added chemicals. However, the problems are still poorly understood because of the "what organic constituents are contained in the low rank coals"! This not only hinders the development of coal science, but also more severely limits the high value-added utilization of low-rank coal.
Revealing the composition structure of organic matters of low-rank coal from the molecular level is always the direction of effort of coal scientists, and solvent extraction is an important means for researching the coal structure, but because the solvent extraction of coal is solid-liquid extraction, the time consumption is long, and researchers utilize CS2The extraction rate of the Longkou lignite is continuously increased after 1600 hours of extraction. During fractional extraction, the components in the first-stage solvent soluble substance are more likely to appear in the second-stage extract and even the third-stage extract, so that the extraction time is long and the complete extraction is difficult to become a bottleneck for restricting the quantitative analysis of the organic matters in the low-rank coal. The prior extraction technology does not have a good solution to the problems.
Disclosure of Invention
Aiming at the problems existing in the prior art: the extraction time in the coal solid-liquid extraction technology is long, and complete extraction is difficult.
The invention provides aqueous alkali liquid extraction of low-rank coal.
A low-rank coal aqueous alkaline hydrolysis liquid extraction method comprises the following steps:
s1 coal sample crushing: crushing, sieving, dividing, vacuum drying, sealing and storing the coal sample;
hydrolysis and alkaline depolymerization of S2: putting the coal sample prepared in the S1, water and alkali into a high-pressure kettle, sealing and heating to obtain a depolymerized mixture;
s3 filtering: filtering the depolymerization mixture obtained in the step S2 to obtain filtrate which is coal depolymerization;
s4 liquid-liquid extraction: and (4) adding the coal depolymerization product obtained in the step (S3) into a separating funnel, and adding an extracting agent for liquid-liquid extraction to obtain a liquid-liquid extract and a raffinate.
S5 micro solid-liquid extraction: and adding an extracting agent into the raffinate obtained in the step S4, adding acid to the raffinate to be acidic, and extracting to obtain a micro solid-liquid extract.
Wherein, in S1, the coal sample is crushed to 80-300 meshes, and the vacuum drying temperature is 50-105 ℃; the reaction temperature is 105-250 ℃; the depolymerization time is 0.2-2 h; the pressure is the heating self-pressurization force of the closed reaction kettle.
Wherein, the alkali is NaOH or KOH.
Wherein the addition amount of the water is 30-200mL/g coal; the amount of alkali is 0.2-0.6 g/g coal.
Wherein, the extraction solvent comprises: petroleum ether, n-hexane, cyclohexane, carbon disulfide, dichloromethane, chloroform, benzene, toluene, ethyl acetate, diethyl ether, cyclohexanone or their mixed solvent; single stage extraction or staged extraction may be employed.
Wherein, the S5 is assisted by ultrasonic dispersion; adding acid to adjust pH to 0-6.
Preferably, in S1, the coal sample is crushed to 150-200 meshes, and the vacuum drying temperature is 90-105 ℃.
Preferably, in S2, the water is added in an amount of 20-200 mL/g coal, the used alkali is NaOH, the depolymerization temperature is 120-210 ℃, and the depolymerization time is 0.5-1 h.
Preferably, in S4, single-stage extraction with petroleum ether, dichloromethane, benzene, ethyl acetate, or fractional extraction with petroleum ether, dichloromethane, benzene, ethyl acetate in sequence may be performed.
Preferably, in S5, petroleum ether, dichloromethane, benzene or ethyl acetate extractant with 2-5 times volume of the coal depolymerization solution is added, and the pH value is adjusted to 1-3 under the assistance of ultrasonic wave, and the extraction is carried out for 0.5-2 hours. Further, fractional extraction with petroleum ether, dichloromethane, benzene, ethyl acetate may be carried out in this order.
The coal is subjected to high-temperature and high-pressure treatment to obtain the coal water alkaline hydrolysis solution. The liquid-liquid extraction is used, the extraction efficiency is greatly improved, and non/weak polar small molecular organic matters which are mostly normal alkanes are obtained. Further, the pH is adjusted to be acidic, so that coal depolymerization is re-associated to form a tiny solid cluster and is separated out, and tiny solid-liquid extraction is carried out, at the moment, a non-polar compound is not easily associated into solid particles with strong polarity and is easy to enter an organic solvent phase, so that more organic structures, namely, naphthene and aromatic hydrocarbon, are obtained by extraction.
Drawings
FIG. 1 is a flow diagram of liquid-liquid extraction and micro-solid-liquid extraction.
Detailed Description
In order to clearly express the technical features of the invention, the invention is explained in detail by the specific embodiments and the attached drawings.
The detailed description is not intended to limit the scope of the invention, and any alternative modifications or variations to the embodiments of the invention are intended to fall within the scope of the invention.
Example 1:
s1, crushing a coal sample: crushing the victory lignite to 200 meshes, dividing, then drying in vacuum for 5 h at 100 ℃, sealing and storing.
S2, hydrolysis and alkaline depolymerization: 10 g of victory lignite is put into an autoclave, 200mL of water and 5 g of NaOH are added, the autoclave is sealed, and the reaction is heated to 180 ℃ for 1 h to obtain a reaction mixture.
S3, filtering: and (4) filtering and separating the reaction mixture obtained in the S2 to obtain filtrate, namely the coal depolymerization product.
S4, liquid-liquid extraction: the coal depolymerization product obtained in S3 was put into a 1000 mL separatory funnel, and 600 mL petroleum ether was added to conduct liquid-liquid extraction, and the extraction was repeated 5 times to obtain 0.1 g of petroleum ether extract and raffinate.
S5, micro solid-liquid extraction: 600 mL of benzene was added to the raffinate obtained in S4 with the aid of ultrasonic waves, and hydrochloric acid was added to adjust the pH to 1, and extraction was repeated 5 times to obtain 0.08 g of a benzene extract.
Through gas chromatography/mass spectrometry analysis, the petroleum ether extract is mainly normal alkane, and the benzene extract detects a plurality of long-chain cyclane and arene and detects a plurality of diethyl alkane which are reported rarely.
Example 2:
s1, crushing a coal sample: the method comprises the steps of crushing the east-west bituminous coal to 200 meshes, dividing, drying in vacuum for 5 hours at 100 ℃, and sealing and storing.
S2, hydrolysis and alkaline depolymerization: 20 g of eastern subbituminous coal was placed in an autoclave, 300 mL of water and 8 g of NaOH were added, the autoclave was sealed, and the reaction mixture was obtained by heating to 200 ℃ for 1 hour.
S3, filtering: and (4) filtering and separating the reaction mixture obtained in the S2 to obtain filtrate, namely the coal depolymerization product.
S4, liquid-liquid extraction: the coal depolymerization product obtained in S3 was put into a 1000 mL separatory funnel, and 600 mL of ethyl acetate was added to conduct liquid-liquid extraction, and the extraction was repeated 10 times to obtain 0.1 g of an ethyl acetate extract.
Through gas chromatography/mass spectrometry analysis, the ethyl acetate extract contains a series of normal alkanes, alkenes, aromatics, methyl ketone and ethyl ketone, and a newly reported long-chain alkanal is detected.
Claims (6)
1. The extraction method of the low-rank coal alkaline hydrolysis liquid is characterized by comprising the following steps of:
s1 coal sample crushing: crushing, sieving, dividing, vacuum drying, sealing and storing the coal sample;
hydrolysis and alkaline depolymerization of S2: putting the coal sample prepared in the step S1, water and alkali into a high-pressure kettle, sealing, heating, and obtaining a depolymerized mixture under high temperature and high pressure;
s3 filtering: filtering the depolymerization mixture obtained in the step S2 to obtain filtrate which is coal depolymerization;
s4 liquid-liquid extraction: adding the coal depolymerization product obtained in the step S3 into a separating funnel, and adding an extracting agent for liquid-liquid extraction to obtain a liquid-liquid extract and an extraction residue;
s5 micro solid-liquid extraction: and adding an extracting agent into the raffinate obtained in the step S4, adding acid to the raffinate to be acidic, and extracting to obtain a micro solid-liquid extract.
2. The method of claim 1, wherein in S1, the coal sample is crushed to 80-300 mesh, and the vacuum drying temperature is 50-105 ℃; the reaction temperature is 105-250 ℃; the depolymerization time is 0.2-2 h.
3. The method of claim 1, wherein the base is NaOH or KOH.
4. The method of claim 1, wherein said water is added in an amount of 30-150 mL/gCoal (coal)(ii) a The alkali dosage is 0.05-0.3 g/gCoal (coal)。
5. The method of claim 1, wherein: the extraction solvent comprises: petroleum ether, n-hexane, cyclohexane, carbon disulfide, dichloromethane, chloroform, benzene, toluene, ethyl acetate, diethyl ether, cyclohexanone or their mixed solvent; single stage extraction or staged extraction may be employed.
6. The method according to claim 1, wherein said S5 is supplemented with ultrasonic dispersion; adding acid to adjust pH to 0-6.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1964989B1 (en) * | 1969-12-24 | 1970-11-05 | Metallgesellschaft Ag | Process for the purification of the aqueous raffinate phase resulting from the solvent extraction of aqueous metal salt solutions |
| US4539095A (en) * | 1984-04-19 | 1985-09-03 | Air Products And Chemicals, Inc. | Aqueous alkali depolymerization of coal with a quinone |
| US4539094A (en) * | 1984-04-19 | 1985-09-03 | Air Products And Chemicals, Inc. | Extraction of depolymerized carbonaceous material using supercritical ammonia |
| CN103881752A (en) * | 2014-04-12 | 2014-06-25 | 曲靖众一精细化工股份有限公司 | Method and device for leaching high-quality lignite wax |
| CN106422404A (en) * | 2016-09-30 | 2017-02-22 | 安徽工业大学 | Grading preparation method of coal thermal dissolution substance |
| CN107510955A (en) * | 2017-08-31 | 2017-12-26 | 华中科技大学 | A kind of low-order coal hot solvent extracts method for upgrading |
| CN109735375A (en) * | 2019-02-25 | 2019-05-10 | 中国矿业大学 | A kind of high hydrostatic pressure extraction method for Soluble Organic Components of Deep Source in coal |
-
2020
- 2020-12-03 CN CN202011393574.1A patent/CN112587957A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1964989B1 (en) * | 1969-12-24 | 1970-11-05 | Metallgesellschaft Ag | Process for the purification of the aqueous raffinate phase resulting from the solvent extraction of aqueous metal salt solutions |
| US4539095A (en) * | 1984-04-19 | 1985-09-03 | Air Products And Chemicals, Inc. | Aqueous alkali depolymerization of coal with a quinone |
| US4539094A (en) * | 1984-04-19 | 1985-09-03 | Air Products And Chemicals, Inc. | Extraction of depolymerized carbonaceous material using supercritical ammonia |
| CN103881752A (en) * | 2014-04-12 | 2014-06-25 | 曲靖众一精细化工股份有限公司 | Method and device for leaching high-quality lignite wax |
| CN106422404A (en) * | 2016-09-30 | 2017-02-22 | 安徽工业大学 | Grading preparation method of coal thermal dissolution substance |
| CN107510955A (en) * | 2017-08-31 | 2017-12-26 | 华中科技大学 | A kind of low-order coal hot solvent extracts method for upgrading |
| CN109735375A (en) * | 2019-02-25 | 2019-05-10 | 中国矿业大学 | A kind of high hydrostatic pressure extraction method for Soluble Organic Components of Deep Source in coal |
Non-Patent Citations (3)
| Title |
|---|
| XING SHUN CONG: "《Unambiguous Evidence for the Occurrence of Pentamethylphenol in Lignite Methanolysate》", 《ENERGY ＆ FUELS》 * |
| 丛兴顺 等: "《胜利褐煤水热解聚物中正构烷基环戊烷的富集与分析》", 《枣庄学院学报》 * |
| 肖钢 等: "《能源工程技术丛书 煤中挥发分 另一种形式的石油馈赠》", 31 October 2015, 武汉大学出版社 * |
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Application publication date: 20210402 |