CN104830363A - Coal direct liquefaction method - Google Patents

Coal direct liquefaction method Download PDF

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Publication number
CN104830363A
CN104830363A CN201510199032.3A CN201510199032A CN104830363A CN 104830363 A CN104830363 A CN 104830363A CN 201510199032 A CN201510199032 A CN 201510199032A CN 104830363 A CN104830363 A CN 104830363A
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coal
liquefaction
microwave
mixture
reaction
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CN201510199032.3A
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蔺华林
韩生
高峰
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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Abstract

The invention discloses a coal direct liquefaction method. The method includes: firstly calculating, by weight percentage, 100-200 mesh pulverized coal, a hydrogen-donor solvent tetrahydronaphthalene, a catalyst Fe2O3 and an assistant elemental sulfur in a ratio of 36%:60%:2%:2%, mixing the 100-200 mesh pulverized coal, the hydrogen-donor solvent tetrahydronaphthalene, the catalyst Fe2O3 and the assistant elemental sulfur evenly, subjecting the mixture to microwave treatment at set power of 0.3-0.5KW for 10-15min, then transferring the mixture into a high-pressure reaction kettle, then adding tetrahydronaphthalene accounting for 10% of the total mass of the mixture, under hydrogen protection, controlling the temperature at 350-400DEG C and the pressure at 5-8MPa, carrying out liquefaction reaction for 30-60min, subjecting the reaction liquid to Soxhlet extraction, and then collecting n-hexane soluble substance so as to obtain liquefied oil. According to the method, the reaction pressure and temperature are low, the energy consumption and unsafe factors are reduced, and the final coal conversion rate and liquefied oil yield are high.

Description

A kind of method of DCL/Direct coal liquefaction
Technical field
The present invention relates to a kind of method of DCL/Direct coal liquefaction, obtain coal Direct Hydrogenation liquefaction reaction product and liquefaction oil.The method liquefaction reaction temperature and pressure is lower, and the transformation efficiency of coal, the yield of liquefaction oil are all higher.
Background technology
Coal plays an important role in Chinese national economy evolution as important fuel and industrial chemicals.In following 30 ~ 50 years, China's primary energy source is produced, consumption will based on coal, burning is still main use-pattern, coal contains the objectionable impuritiess such as sulphur, chlorine, nitrogen, ash and is discharged into after coal directly burns in environment, cause serious problem of environmental pollution, China has become one of country that environmental pollution is the most serious in the world.Therefore; no matter from the reduction energy and economic security angle; or alleviating consideration in environmental protection pressure; make full use of the coal resources advantage of China's abundant; greatly develop the new high-tech industry of " replace oil with coal, make oil with coal "; be optimize state energy structure, reduce petroleum import interdependency, the important channel of the Sustainable development of protection of the environment, maintenance national economy, have great importance.
Technology of direct coal liquefaction increases liquid energy product-feed, reduces one of effective way that oil relies on; Coal direct liquefaction is in High Temperature High Pressure, faces under hydrogen, solvent and catalyzer exist, and coal hydrogenation cracking generates the technological process of liquid product.
At present consistent viewpoint is basically formed for coal liquefaction, think in Coal Liquefaction process, coal molecule decomposes produces unstable free radical, under having enough hydrogen to exist, free radical just can obtain saturated and settle out, if hydrogen is inadequate or do not have, then be combined with each other between free radical and change insoluble Jiao into.In general, this process can be divided into the heat of solution of coal, hydrogen transference and hydrogenation three steps.But there is following shortcoming in traditional coal direct liquefaction method:
Temperature of reaction, pressure are higher, and temperature is generally 440-460 DEG C, and pressure is generally 9-10MPa, and therefore energy consumption is high, and the required pressure of reaction is high, adds unsafe factor, and also high to the requirement of equipment.
Summary of the invention
There is the technical problems such as high energy consumption, high risk, yield be low and a kind of method that DCL/Direct coal liquefaction is provided in object of the present invention to solve above-mentioned traditional coal direct liquefaction method, the method utilizes microwave to process in advance raw material, and then liquefaction reaction is carried out in autoclave, therefore to have the pressure and temperature of reaction low for the method, thus decrease energy consumption and unsafe factor, the transformation efficiency of final coal can reach 95.35-96.33%, and liquefaction oil yield can reach 66.54-75.15%.
Technical scheme of the present invention
A method for DCL/Direct coal liquefaction, step is as follows:
First count by weight percentage, namely cross the coal dust of 100 ~ 200 mesh sieves: hydrogen supply dissolvent naphthane: catalyst Fe 2o 3: auxiliary agent elemental sulfur is the ratio of 36%:60%:2%:2%, will cross coal dust, hydrogen supply dissolvent naphthane, the catalyst Fe of 100 ~ 200 mesh sieves 2o 3mix with auxiliary agent elemental sulfur, be placed on by mixture in microwave experiment stove, setting power is 0.3-0.5KW, microwave treatment 10-15min;
Above-mentioned use microwave scientific experiment stove, but the present invention is not limited to this, as: microwave kiln, the device that general household microwave oven etc. can produce microwave is all alternative;
Then transferred in autoclave by mixture, then add naphthane, the add-on of naphthane is 10% of mixture total mass, under hydrogen shield, and control temperature 350-400 DEG C, to carry out the liquefaction reaction time be 30-60min to pressure 5-8MPa, obtains reaction solution;
Finally by the reaction solution of above-mentioned gained after soxhlet type, collect normal hexane solvend and be liquefaction oil.
beneficial effect of the present invention
The method of a kind of DCL/Direct coal liquefaction of the present invention, adopt microwave treatment in advance owing to preparing raw material used, thus the macromolecular network structure of coal is loosened, rupture some cross-link bond, increase solvent contacts with coal, and catalyzer small molecules is more easily entered in the molecular structure of reactant.Coal after microwave treatment carry out liquefaction reaction again, increase contacting of coal dust and hydrogen supply dissolvent, granules of catalyst is more easily contacted with reactant, therefore finally can reduce the pressure and temperature of reaction, thus decrease energy consumption and the unsafe factor of production.
Further, the method for a kind of DCL/Direct coal liquefaction of the present invention, the transformation efficiency of coal is high, can reach more than 95%, i.e. the method for DCL/Direct coal liquefaction of the present invention, and the utilization ratio of feed coal is high.
Further, the method for a kind of DCL/Direct coal liquefaction of the present invention, easy and simple to handle, solvent for use is easy to get, thus production cost is low, is beneficial to suitability for industrialized production.
Embodiment
Below by specific embodiment, the present invention is set forth further, but do not limit the present invention.
In embodiments of the invention, the method for measuring of coal transformation efficiency, liquefaction oil yield etc. is see Guo Zhi, Shi Shidong, Wang Yong etc., the dynamics research of Firing Shenhua Coal autoclave hydrogenation liquefaction isothermal reaction, coal conversion, 2007,30(3): 34-36;
In embodiments of the invention, the calculation formula of coal transformation efficiency, liquefaction oil yield etc. is as follows:
The coal sample quality X100% of coal transformation efficiency=(total coal sample quality-non-reacted parts coal sample quality)/total.
The raw coal sample quality X100% of liquefaction oil yield=(raw coal sample-normal hexane insolubles)/total.
Coal dust used in various embodiments of the present invention is upper gulf coal coal dust.
embodiment 1
A method for DCL/Direct coal liquefaction, step is as follows:
First count by weight percentage, namely cross the coal dust of 100 ~ 200 mesh sieves: hydrogen supply dissolvent naphthane: catalyst Fe 2o 3: auxiliary agent elemental sulfur is the ratio of 36%:60%:2%:2%, 36g is crossed the coal dust of 100 ~ 200 mesh sieves, 60g hydrogen supply dissolvent naphthane, 2g catalyst Fe 2o 3be mix in the furnace pot of 100mm at diameter with 2g auxiliary agent elemental sulfur, obtain mixture, be placed on by gained mixture in microwave experiment stove, setting power is that 0.4KW carries out microwave treatment 15min;
Then transferred to by mixture in 500ml high-pressure mini reactor, add 10g naphthane, under hydrogen shield, control temperature 350 DEG C, pressure 8MPa carry out liquefaction reaction 30min, obtain reaction solution;
Finally by the reaction solution of above-mentioned gained after soxhlet type, collect normal hexane solvend and be liquefaction oil, the extracting of normal hexane insoluble part tetrahydrofuran (THF), the transformation efficiency finally obtaining coal sample is 96.35%, and liquefaction oil yield is 75.15%.
embodiment 2
A method for DCL/Direct coal liquefaction, step is as follows:
First count by weight percentage, namely cross the coal dust of 100 ~ 200 mesh sieves: hydrogen supply dissolvent naphthane: catalyst Fe 2o 3: auxiliary agent elemental sulfur is the ratio of 36%:60%:2%:2%, 36g is crossed the coal dust of 100 ~ 200 mesh sieves, 60g hydrogen supply dissolvent naphthane, 2g catalyst Fe 2o 3be mix in the furnace pot of 100mm at diameter with 2g auxiliary agent elemental sulfur, obtain mixture, be placed on by gained mixture in microwave experiment stove, setting power is that 0.4KW carries out microwave treatment 15min;
Then transferred to by mixture in 500ml high-pressure mini reactor, add 10g naphthane, under hydrogen shield, control temperature 400 DEG C, pressure 4MPa carry out liquefaction reaction 30min, obtain reaction solution;
Finally by the reaction solution of above-mentioned gained after soxhlet type, collect normal hexane solvend and be liquefaction oil, the extracting of normal hexane insoluble part tetrahydrofuran (THF), the transformation efficiency that can obtain coal sample is 95.61%, and liquefaction oil yield is 68.33%.
embodiment 3
A method for DCL/Direct coal liquefaction, step is as follows:
First count by weight percentage, namely cross the coal dust of 100 ~ 200 mesh sieves: hydrogen supply dissolvent naphthane: catalyst Fe 2o 3: auxiliary agent elemental sulfur is the ratio of 36%:60%:2%:2%, 36g is crossed the coal dust of 100 ~ 200 mesh sieves, 60g hydrogen supply dissolvent naphthane, 2g catalyst Fe 2o 3be mix in the furnace pot of 100mm at diameter with 2g auxiliary agent elemental sulfur, obtain mixture, be placed on by gained mixture in microwave experiment stove, setting power is that 0.4KW carries out microwave treatment 15min;
Then transferred to by mixture in 500ml high-pressure mini reactor, add 10g naphthane, under hydrogen shield, control temperature 400 DEG C, pressure 7MPa carry out liquefaction reaction 30min, obtain reaction solution;
Finally by the reaction solution of above-mentioned gained after soxhlet type, collect normal hexane solvend and be liquefaction oil, the extracting of normal hexane insoluble part tetrahydrofuran (THF), the transformation efficiency that can obtain coal sample is 95.33%, and liquefaction oil yield is 66.54%.
comparative examples 1
A method for DCL/Direct coal liquefaction, step is as follows:
First count by weight percentage, namely cross the coal dust of 100 ~ 200 mesh sieves: hydrogen supply dissolvent naphthane: catalyst Fe 2o 3: auxiliary agent elemental sulfur is the ratio of 36%:60%:2%:2%, 36g is crossed the coal dust of 100 ~ 200 mesh sieves, 60g hydrogen supply dissolvent naphthane, 2g catalyst Fe 2o 3be mix in the furnace pot of 100mm at diameter with 2g auxiliary agent elemental sulfur, obtain mixture;
Then transferred to by mixture in 500ml high-pressure mini reactor, add 10g naphthane, under hydrogen shield, control temperature 440 DEG C, pressure 9MPa carry out the anti-30min that liquefies, and obtain reaction liquid;
Finally by the reaction solution of above-mentioned gained after soxhlet type, collect normal hexane solvend and be liquefaction oil.
Coal transformation efficiency, liquefaction oil yield, gas productive rate, aquatic products rate, asphaltene productive rate and hydrogen consumption in above-described embodiment 1 and comparative examples 1 preparation process is measured respectively, the results are shown in following table:
Test item Embodiment 1 Embodiment 2 Embodiment 3 Comparative examples 1
Temperature of reaction/DEG C 350 400 400 440
Reaction pressure/MPa 8 5 7 9
Coal transformation efficiency (%) 95.35 95.61 96.33 84.23
Liquefaction oil yield (%) 75.15 68.33 66.54 53.33
As can be seen from the above table, relative to the coal sample crossed without microwave treatment, liquefaction reaction is carried out again after microwave treatment, even if temperature is not high, pressure is not high, also can have good coal sample transformation efficiency and liquefaction oil yield, the transformation efficiency of final coal can reach 95.35-96.33%, and liquefaction oil yield can reach 66.54-75.15%.
In sum, the method of a kind of DCL/Direct coal liquefaction of the present invention, first coal sample naphthane dissolves by the method, Coal liquefaction is carried out again again after microwave treatment, with not compared with the microwave treatment, there is higher transformation efficiency and oily yield, even if under the condition that temperature is slightly low and pressure is slightly low, also have higher transformation efficiency and oily yield.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement, these improvement also should be considered as protection scope of the present invention.

Claims (4)

1. a method for DCL/Direct coal liquefaction, is characterized in that concrete steps are as follows:
First count by weight percentage, namely cross the coal dust of 100 ~ 200 mesh sieves: hydrogen supply dissolvent naphthane: catalyst Fe 2o 3: auxiliary agent elemental sulfur is the ratio of 36%:60%:2%:2%, will cross coal dust, hydrogen supply dissolvent naphthane, the catalyst Fe of 100 ~ 200 mesh sieves 2o 3mix with auxiliary agent elemental sulfur, be placed on by mixture in microwave experiment stove, setting power is 0.3-0.5KW, microwave treatment 10-15min;
Then transferred in autoclave by mixture, then add naphthane, the add-on of naphthane is 10% of mixture total mass, under hydrogen shield, and control temperature 350-400 DEG C, pressure 5-8MPa carries out liquefaction reaction 30-60min, obtains reaction solution;
Finally by the reaction solution of above-mentioned gained after soxhlet type, collect normal hexane solvend and be liquefaction oil.
2. the method for a kind of DCL/Direct coal liquefaction as claimed in claim 1, is characterized in that described microwave scientific experiment stove microwave kiln substitutes.
3. the method for a kind of DCL/Direct coal liquefaction as claimed in claim 1, is characterized in that the described microwave scientific experiment stove device that can produce microwave substitutes.
4. the method for a kind of DCL/Direct coal liquefaction as claimed in claim 1, it is characterized in that described power is 0.4KW, microwave treatment time is 15min.
CN201510199032.3A 2015-04-24 2015-04-24 Coal direct liquefaction method Pending CN104830363A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106916611A (en) * 2015-12-28 2017-07-04 中科合成油技术有限公司 A kind of method pre-processed to the coal reacted for DCL/Direct coal liquefaction
WO2023009788A1 (en) * 2021-07-30 2023-02-02 Qwave Solutions, Inc. Methods and systems for liquefaction of carbonaceous materials

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06108061A (en) * 1992-09-25 1994-04-19 Nippon Steel Corp Liquefaction of coal
CN101429440A (en) * 2007-07-25 2009-05-13 汉能科技有限公司 Method for direct liquefaction of coal
CN103834426A (en) * 2014-03-20 2014-06-04 上海应用技术学院 Method for producing liquefied oil by directly hydro-liquefy coal in presence of ionic liquid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06108061A (en) * 1992-09-25 1994-04-19 Nippon Steel Corp Liquefaction of coal
CN101429440A (en) * 2007-07-25 2009-05-13 汉能科技有限公司 Method for direct liquefaction of coal
CN103834426A (en) * 2014-03-20 2014-06-04 上海应用技术学院 Method for producing liquefied oil by directly hydro-liquefy coal in presence of ionic liquid

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Title
HENGFU SHUI ET AL: "Effect of pre-swelling of coal on its solvent extraction and liquefaction properties", 《FUEL》 *
郭靖等: "微波溶胀对五彩湾煤直接液化影响的研究", 《当代化工》, vol. 39, no. 4, 31 August 2010 (2010-08-31), pages 369 - 371 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106916611A (en) * 2015-12-28 2017-07-04 中科合成油技术有限公司 A kind of method pre-processed to the coal reacted for DCL/Direct coal liquefaction
WO2023009788A1 (en) * 2021-07-30 2023-02-02 Qwave Solutions, Inc. Methods and systems for liquefaction of carbonaceous materials
US11827854B2 (en) 2021-07-30 2023-11-28 Qwave Solutions, Inc. Methods and systems for liquefaction of carbonaceous materials

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Application publication date: 20150812