CN103589444A - Methanol mixed solvent pretreatment method for direct coal hydro-liquefaction - Google Patents
Methanol mixed solvent pretreatment method for direct coal hydro-liquefaction Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003245 coal Substances 0.000 title claims abstract description 108
- 239000012046 mixed solvent Substances 0.000 title claims abstract description 43
- 238000002203 pretreatment Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 238000007701 flash-distillation Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006073 displacement reaction Methods 0.000 claims description 10
- 238000005194 fractionation Methods 0.000 claims description 10
- 238000010298 pulverizing process Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- -1 and in still Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003250 coal slurry Substances 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000007859 condensation product Substances 0.000 description 16
- 230000009466 transformation Effects 0.000 description 13
- 239000003077 lignite Substances 0.000 description 12
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 206010042674 Swelling Diseases 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 239000009798 Shen-Fu Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012453 solvate Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003476 subbituminous coal Substances 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明提供一种煤直接加氢液化的甲醇混合溶剂前处理方法，属于煤直接液化技术领域。该方法是按溶剂/煤质量比为2～5，将粉碎后的原煤和一种甲醇混合溶剂，加入到带闪蒸装置的高压反应釜中，在0.1～2MPa N2气氛中，250～350℃恒温热处理30～180min；然后经闪蒸冷凝分离出溶剂和轻质组分，所得处理煤冷却后，直接加入液化溶剂和催化剂制备液化煤浆，用于直接加氢液化。同时，闪蒸冷凝液经蒸馏分离，所得的溶剂循环使用。该方法具有良好的脱水改质作用，直接液化转化率较未处理煤提高10%以上，同时可以获得4%以上的轻质组分。此外，该方法具有成本低、工艺流程短、操作简便、过程清洁等特点。The invention provides a methanol mixed solvent pretreatment method for direct coal hydrogenation liquefaction, belonging to the technical field of direct coal liquefaction. The method is to add the pulverized raw coal and a methanol mixed solvent into a high-pressure reaction kettle with a flash evaporation device according to the solvent/coal mass ratio of 2 to 5, and in an atmosphere of 0.1 to 2 MPa N2 , 250 to 350 Heat treatment at constant temperature at ℃ for 30-180 minutes; then flash condensation to separate the solvent and light components, after the treated coal is cooled, directly add liquefaction solvent and catalyst to prepare liquefied coal slurry for direct hydrogenation liquefaction. At the same time, the flash condensate is separated by distillation, and the resulting solvent is recycled. The method has a good dehydration and upgrading effect, and the direct liquefaction conversion rate is increased by more than 10% compared with untreated coal, and at the same time, more than 4% of light components can be obtained. In addition, the method has the characteristics of low cost, short process flow, easy operation and clean process.
Description
Technical field
The invention belongs to direct coal liquefaction technology field, be specifically related to a kind of methanol mixed solvent pre-treating process of DCL/Direct coal liquefaction.
Background technology
DCL/Direct coal liquefaction also claims hydrogenation liquefaction, refers generally to, in the hydrogen and hydrogen supply dissolvent of high temperature, high pressure, coal be carried out to pyrolysis, shortening and hydrocracking, makes solid coal be converted into the technological process of liquid oils.Direct coal liquefaction technology can be produced liquid fuel, makes up petroleum resources shortage, has very important realistic meaning and strategic value.
Because coal hydrogenation reactivity is lower, DCL/Direct coal liquefaction reaction needed just can complete under 400～450 ℃ of high temperature and condition of high voltage more than 10MPa.Meanwhile, direct liquefaction feed coal generally adopts the middle low-rank coal of active higher brown coal to the bituminous coal stage.Due to middle or low price moisture content of coal content and oxygen level higher, reactive hydrogen consumption and energy consumption are high, are one of key factors restricting DCL/Direct coal liquefaction.So by the pre-treatment of coal, improve Coal Liquefaction reactive, reduce moisture and the oxygen level of coal, be conducive to promote the efficient liquefaction of coal.For example: in the brown coal liquefaction process (BCL) of Japanese NEDO for Australian high-moisture brown coal liquefaction exploitation, adopted the pre-treating technology of liquefaction solvent dehydration.
Because DCL/Direct coal liquefaction belongs to heterogeneous reaction, mass transfer process remarkably influenced Coal Liquefaction.Coal has macromolecular structure feature, wherein not only has the covalently cross-linked of complexity, and has a large amount of non covalent bond crosslinked actions such as hydrogen bond.So Macromolecule in coal structure must could promote hydrogen supply dissolvent, catalyzer and dissolve H after abundant swelling
2coal and pyrolysis product thereof are carried out to hydrogenation.Patent CN101787310 provides a kind of brown coal pretreatment process, utilizes methyl alcohol to carry out supercritical extraction to brown coal, and the extract remainder of isolating after extraction liquid liquefies for thermally dissolving and catalytic.Found that, supercritical methanol pre-treatment can change brown coal microvoid structure, augmenting response specific surface area, the transformation efficiency of raising brown coal.Yet, because methanol solvate polarity is strong, poor to the wetting capacity of coal, especially the higher sub-bituminous coal in coal rank is infiltrated and swelling ability, so carry out needing certain pre-swelling treatment before supercritical methanol processing.
The present invention, according to the constructional feature of coal, provides a kind of methanol mixed solvent pre-treating process of coal Direct Hydrogenation liquefaction.By adding a kind of aromatic solvent, improve methanol solvate to the infiltration of middle or low price coal and swelling ability, without pre-swelling treatment, and can change mixed solvent composition, the strong adaptability to coal according to coal.Meanwhile, adopt flash evaporation to carry out separated from solvent, gained is processed coal can directly prepare liquefaction coal slurry, is directly used in liquefaction, and has the effect that simultaneously removes water, solvent and light component.In addition, the present invention is without adding any soda acid in pretreatment process, and gained mixed solvent can recycle after separation for phlegma, and technological process is clean, simple.
Summary of the invention
The object of this invention is to provide a kind of methanol mixed solvent pre-treating process that improves DCL/Direct coal liquefaction efficiency.By high temperature methanol mixed solvent treatment, the non covalent bond effect of macromolecular structure in lax raw coal, improves infiltration and the swelling ability of coal, improves the mass transfer ability of hydrogen supply dissolvent, hydrogen and catalyzer, promotes the hydrocracking of coal.
The methanol mixed solvent pre-treating process concrete steps of a kind of coal Direct Hydrogenation liquefaction provided by the present invention are as follows:
(1) pre-treatment: the raw coal after pulverizing is added in the autoclave with flash distillation plant, and the ratio that is 2～5 in solvent/coal mass ratio adds methanol mixed solvent, and in still, air is through N
2after displacement, utilize N
2adjusting reacting kettle inner pressure is 0.1～2MPa, then opens and stirs, and be warming up to 250～350 ℃, and constant temp. heating is processed 30～180min; Described methanol mixed solvent is comprised of methyl alcohol and a kind of aromatic hydrocarbons, described aromatic hydrocarbons nail benzene or dimethylbenzene, and in mixed solvent, the volume fraction of aromatic hydrocarbons is 10～40%;
(2) separation: when step (1) finishes, stop stirring, standing 5min under treatment temp, then, slowly open relief valve, coal and still internal solvent and light component are carried out to flash separation, isolated solvent and light component are collected after condenser is cooling, until still internal pressure, be down to after normal pressure, stop heating, and naturally cooling obtain pre-treatment coal;
(3) liquefaction: treat that in autoclave, pre-treatment coal is cooled to below 100 ℃, carry out hydrogenation liquefaction.
Further, the flash distillation phlegma that in described step (2), condenser is collected can obtain respectively mixed solvent and light component through fractionation by distillation, and described isolated mixed solvent can be recycled.
Compared with prior art, the present invention has following technique effect:
1, the invention provides a kind of methanol mixed solvent pre-treating process of DCL/Direct coal liquefaction, compare with raw coal, methanol mixed solvent pre-treatment gelatin liquefaction transformation efficiency improves more than 10%, and moisture reduction reaches more than 80%, and can separation obtain a certain amount of light component;
2, by adding a kind of aromatic solvent, improve methanol solvate to the infiltration of middle or low price coal and swelling ability, without pre-swelling treatment, and can change mixed solvent composition, the strong adaptability to coal according to coal;
3, adopt flash evaporation to carry out separated from solvent, gained is processed coal can directly prepare liquefaction coal slurry, for direct liquefaction, and has the effect that simultaneously removes water, solvent and light component;
4, in pretreatment process without adding any soda acid, the mixed solvent of phlegma gained after separation can recycle, technological process is simple, clean.
Embodiment
In order further to understand technology contents of the present invention, below by specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Reference examples 1: add successively 10.0g shenfu coal raw coal in 200ml high-pressure reactor, 0.5g catalyzer (being formed mol ratio 1 by FeS and S), 25ml hydrogen supply dissolvent naphthane.After closed reactor with H
2purge 3 times, air in metathesis reactor, and be filled with H after pressure testing, leak detection
2to 5MPa.Then with 10～15 ℃/min heating rate, reactor is heated to 400 ℃, and under 400 ℃ of conditions constant temperature liquefaction 60min.Finally, reactor cooling, to room temperature, is taken out to liquefied product, and with tetrahydrofuran (THF) washing reaction still, all liquefied product be take tetrahydrofuran (THF) and are carried out Soxhlet extracting as solvent subsequently.According to the THF after 80 ℃ of vacuum-dryings, taking out excess weight calculating shenfu coal direct liquefaction transformation efficiency is 70.8%.Wherein, gelatin liquefaction transformation efficiency method of calculation following (daf refers to that dry ash-free basis is accurate):
Reference examples 2: add successively 10.0g Siklingelei brown coal raw coal in 200ml high-pressure reactor, 0.5g catalyzer (being formed mol ratio 1 by FeS and S), 25ml hydrogen supply dissolvent naphthane.After closed reactor with H
2purge 3 times, air in metathesis reactor, and be filled with H2 to 5MPa after pressure testing, leak detection.Then with 10～15 ℃/min heating rate, reactor is heated to 400 ℃, and under 400 ℃ of conditions constant temperature liquefaction 60min.Finally, reactor cooling, to room temperature, is taken out to liquefied product, and with tetrahydrofuran (THF) washing reaction still, all liquefied product be take tetrahydrofuran (THF) and are carried out Soxhlet extracting as solvent subsequently.According to the THF after 80 ℃ of vacuum-dryings, take out excess weight, calculating Siklingelei brown coal liquefying conversion rate is 74.0%.Wherein, gelatin liquefaction transformation efficiency method of calculation are identical with reference examples 1.
Embodiment 1: take the shenfu coal raw coal 10.0g after pulverizing, add in the 200ml autoclave with flash distillation plant, the ratio that is 2:1 in solvent/coal mass ratio adds methanol mixed solvent (consisting of volume of toluene content 30% methyl alcohol and toluene), with N
2after the interior air of displacement still 2～3 times, utilize N
2reacting kettle inner pressure is adjusted to 1MPa.Then open and stir, and be warming up to 250 ℃, constant temp. heating is processed 120min.When processing finishes, stop stirring standing 5min under treatment temp.Then, slowly open relief valve, rely on still internal pressure to discharge gaseous component in still, and, collection condensation product cooling through flash condenser.Until still internal pressure, to normal pressure, stop heating, and naturally cool to below 100 ℃.Finally, add 25ml naphthane hydrogen supply dissolvent, 0.5g catalyzer (consisting of mol ratio 1 FeS and S), by the coal liquefaction method of reference examples 1, carries out Direct Hydrogenation liquefaction, and recording and processing liquidation of coal transformation efficiency is 86.9%.In addition, flash distillation condensation product reclaims mixed solvent through fractionation by distillation, calculates by analysis light component yield 4.3%wt, pre-treatment coal dewatering rate 87%.
Embodiment 2: take the shenfu coal raw coal 10.0g after pulverizing, add in the 200ml autoclave with flash distillation plant, the ratio that is 3:1 in solvent/coal mass ratio adds methanol mixed solvent (consisting of volume of toluene content 30% methyl alcohol and toluene), with N
2after the interior air of displacement still 2～3 times, utilize N
2reacting kettle inner pressure is adjusted to 0.1MPa.Then open and stir, and be warming up to 350 ℃, constant temp. heating is processed 60min.When processing finishes, stop stirring standing 5min under treatment temp.Then, slowly open relief valve, rely on still internal pressure to discharge gaseous component in still, and, collection condensation product cooling through flash condenser.Until still internal pressure, to normal pressure, stop heating, and naturally cool to below 100 ℃.Finally, add 25ml naphthane hydrogen supply dissolvent, 0.5g catalyzer (consisting of mol ratio 1 FeS and S), by the coal liquefaction method of reference examples 1, carries out Direct Hydrogenation liquefaction, and recording and processing liquidation of coal transformation efficiency is 82.0%.In addition, flash distillation condensation product reclaims mixed solvent through fractionation by distillation, calculates by analysis light component yield 6.9%wt, pre-treatment coal dewatering rate 83%.
Embodiment 3: take the shenfu coal raw coal 10g after pulverizing, add in the 200ml autoclave with flash distillation plant, the ratio that is 5:1 in solvent/coal mass ratio adds methanol mixed solvent (consisting of dimethylbenzene volume content 30% methyl alcohol and dimethylbenzene), with N
2after the interior air of displacement still 2～3 times, utilize N
2reacting kettle inner pressure is adjusted to 1MPa.Then open and stir, and be warming up to 250 ℃, constant temp. heating is processed 180min.When processing finishes, stop stirring standing 5min under treatment temp.Then, slowly open relief valve, rely on still internal pressure to discharge gaseous component in still, and, collection condensation product cooling through flash condenser.Until still internal pressure, to normal pressure, stop heating, and naturally cool to below 100 ℃.Finally, add 25ml naphthane hydrogen supply dissolvent, 0.5g catalyzer (consisting of mol ratio 1 FeS and S), by the coal liquefaction method of reference examples 1, carries out Direct Hydrogenation liquefaction, and recording and processing liquidation of coal transformation efficiency is 87.5%.In addition, flash distillation condensation product reclaims mixed solvent through fractionation by distillation, calculates by analysis light component yield 3.9%wt, pre-treatment coal dewatering rate 79%.
Embodiment 4: take the shenfu coal raw coal 10.0g after pulverizing, add in the 200ml autoclave with flash distillation plant, the ratio that is 2:1 in solvent/coal mass ratio adds methanol mixed solvent (consisting of volume of toluene content 40% methyl alcohol and toluene), with N
2after the interior air of displacement still 2～3 times, utilize N
2reacting kettle inner pressure is adjusted to 2MPa.Then open and stir, and be warming up to 300 ℃, constant temp. heating is processed 90min.When processing finishes, stop stirring standing 5min under treatment temp.Then, slowly open relief valve, rely on still internal pressure to discharge gaseous component in still, and, collection condensation product cooling through flash condenser.Until still internal pressure, to normal pressure, stop heating, and naturally cool to below 100 ℃.Finally, add 25ml naphthane hydrogen supply dissolvent, 0.5g catalyzer (consisting of mol ratio 1 FeS and S), by the coal liquefaction method of reference examples 1, carries out Direct Hydrogenation liquefaction, and recording and processing liquidation of coal transformation efficiency is 88.0%.In addition, flash distillation condensation product reclaims mixed solvent through fractionation by distillation, calculates by analysis light component yield 5.8%wt, pre-treatment coal dewatering rate 85%.
Embodiment 5: take the shenfu coal raw coal 10.0g after pulverizing, add in the 200ml autoclave with flash distillation plant, the ratio that is 3:1 in solvent/coal mass ratio adds methanol mixed solvent (consisting of volume of toluene content 10% methyl alcohol and toluene), with N
2after the interior air of displacement still 2～3 times, utilize N
2reacting kettle inner pressure is adjusted to 1MPa.Then open and stir, and be warming up to 350 ℃, constant temp. heating is processed 30min.When processing finishes, stop stirring standing 5min under treatment temp.Then, slowly open relief valve, rely on still internal pressure to discharge gaseous component in still, and, collection condensation product cooling through flash condenser.Until still internal pressure, to normal pressure, stop heating, and naturally cool to below 100 ℃.Finally, add 25ml naphthane hydrogen supply dissolvent, 0.5g catalyzer (consisting of mol ratio 1 FeS and S), by the coal liquefaction method of reference examples 1, carries out Direct Hydrogenation liquefaction, and recording and processing liquidation of coal transformation efficiency is 82.9%.In addition, flash distillation condensation product reclaims mixed solvent through fractionation by distillation, calculates by analysis light component yield 6.2%wt, pre-treatment coal dewatering rate 87%.
Embodiment 6: take Siklingelei brown coal raw coal 10.0g after pulverizing, add in the 200ml autoclave with flash distillation plant, the ratio that is 3:1 in solvent/coal mass ratio adds methanol mixed solvent (consisting of volume of toluene content 10% methyl alcohol and toluene), with N
2after the interior air of displacement still 2～3 times, utilize N
2reacting kettle inner pressure is adjusted to 1MPa.Then open and stir, and be warming up to 250 ℃, constant temp. heating is processed 120min.When processing finishes, stop stirring standing 5min under treatment temp.Then, slowly open relief valve, rely on still internal pressure to discharge gaseous component in still, and, collection condensation product cooling through flash condenser.Until still internal pressure, to normal pressure, stop heating, and naturally cool to below 100 ℃.Finally, add 25ml naphthane hydrogen supply dissolvent, 0.5g catalyzer (consisting of mol ratio 1 FeS and S), by the coal liquefaction method of reference examples 2, carries out Direct Hydrogenation liquefaction, and recording and processing liquidation of coal transformation efficiency is 86.5%.In addition, flash distillation condensation product reclaims mixed solvent through fractionation by distillation, calculates by analysis light component yield 6.8%wt, pre-treatment coal dewatering rate 89%.
Embodiment 7: take Siklingelei brown coal raw coal 10.0g after pulverizing, add in the 200ml autoclave with flash distillation plant, the ratio that is 5:1 in solvent/coal mass ratio adds methanol mixed solvent (consisting of volume of toluene content 30% methyl alcohol and toluene), with N
2after the interior air of displacement still 2～3 times, utilize N
2reacting kettle inner pressure is adjusted to 0.1MPa.Then open and stir, and be warming up to 300 ℃, constant temp. heating is processed 60min.When processing finishes, stop stirring standing 5min under treatment temp.Then, slowly open relief valve, rely on still internal pressure to discharge gaseous component in still, and, collection condensation product cooling through flash condenser.Until still internal pressure, to normal pressure, stop heating, and naturally cool to below 100 ℃.Finally, add 25ml naphthane hydrogen supply dissolvent, 0.5g catalyzer (consisting of mol ratio 1 FeS and S), by the coal liquefaction method of reference examples 2, carries out Direct Hydrogenation liquefaction, and recording and processing liquidation of coal transformation efficiency is 87.2%.In addition, flash distillation condensation product reclaims mixed solvent through fractionation by distillation, calculates by analysis light component yield 9.5%wt, pre-treatment coal dewatering rate 92%.
Embodiment 8: take Siklingelei brown coal 10.0g after pulverizing, add in the 200ml autoclave with flash distillation plant, the ratio that is 2:1 in solvent/coal mass ratio adds methanol mixed solvent (consisting of dimethylbenzene volume content 10% methyl alcohol and dimethylbenzene), with N
2after the interior air of displacement still 2～3 times, utilize N
2reacting kettle inner pressure is adjusted to 1MPa.Then open and stir, and be warming up to 300 ℃, constant temp. heating is processed 60min.When processing finishes, stop stirring standing 5min under treatment temp.Then, slowly open relief valve, rely on still internal pressure to discharge gaseous component in still, and, collection condensation product cooling through flash condenser.Until still internal pressure, to normal pressure, stop heating, and naturally cool to below 100 ℃.Finally, add 25ml naphthane hydrogen supply dissolvent, 0.5g catalyzer (consisting of mol ratio 1 FeS and S), by the coal liquefaction method of reference examples 2, carries out Direct Hydrogenation liquefaction, and recording and processing liquidation of coal transformation efficiency is 89.8%.In addition, flash distillation condensation product reclaims mixed solvent through fractionation by distillation, calculates by analysis light component yield 7.2%wt, pre-treatment coal dewatering rate 82%.
Claims (2)
1. a methanol mixed solvent pre-treating process for coal Direct Hydrogenation liquefaction, is characterized in that, the method concrete steps are as follows:
(1) pre-treatment: the raw coal after pulverizing is added in the autoclave with flash distillation plant, and the ratio that is 2～5 in solvent/coal mass ratio adds methanol mixed solvent, and in still, air is through N
2after displacement, utilize N
2adjusting reacting kettle inner pressure is 0.1～2MPa, then opens and stirs, and be warming up to 250～350 ℃, and constant temp. heating is processed 30～180min; Described methanol mixed solvent is comprised of methyl alcohol and a kind of aromatic hydrocarbons, described aromatic hydrocarbons nail benzene or dimethylbenzene, and in mixed solvent, the volume fraction of aromatic hydrocarbons is 10～40%;
(2) separation: when step (1) finishes, stop stirring, standing 5min under treatment temp, then, slowly open relief valve, coal and still internal solvent and light component are carried out to flash separation, isolated solvent and light component are collected after condenser is cooling, until still internal pressure, be down to after normal pressure, stop heating, and naturally cooling obtain pre-treatment coal;
(3) liquefaction: treat that in autoclave, pre-treatment coal is cooled to below 100 ℃, carry out hydrogenation liquefaction.
2. the methanol mixed solvent pre-treating process of a kind of coal Direct Hydrogenation liquefaction as claimed in claim 1, it is characterized in that, the flash distillation phlegma that in described step (2), condenser is collected can obtain respectively mixed solvent and light component through fractionation by distillation, and described isolated mixed solvent can be recycled.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106701137A (en) * | 2016-11-25 | 2017-05-24 | 中国矿业大学 | High temperature solvent pretreatment method for improving yield of sodium rich coal direct liquefaction oil |
| CN113583756A (en) * | 2021-08-13 | 2021-11-02 | 北京化工大学 | Method for preparing chemicals and fuel oil by mild hydrogenation liquefaction of medium-low-rank coal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10298557A (en) * | 1997-04-25 | 1998-11-10 | Nippon Steel Corp | Coal liquefaction method |
| CN101643660A (en) * | 2009-01-13 | 2010-02-10 | 煤炭科学研究总院 | Coal liquefaction method |
| CN102936510A (en) * | 2012-10-26 | 2013-02-20 | 安徽工业大学 | Method for extracting higher aliphatic compound from lignite |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10298557A (en) * | 1997-04-25 | 1998-11-10 | Nippon Steel Corp | Coal liquefaction method |
| CN101643660A (en) * | 2009-01-13 | 2010-02-10 | 煤炭科学研究总院 | Coal liquefaction method |
| CN102936510A (en) * | 2012-10-26 | 2013-02-20 | 安徽工业大学 | Method for extracting higher aliphatic compound from lignite |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106701137A (en) * | 2016-11-25 | 2017-05-24 | 中国矿业大学 | High temperature solvent pretreatment method for improving yield of sodium rich coal direct liquefaction oil |
| WO2018095234A1 (en) * | 2016-11-25 | 2018-05-31 | 中国矿业大学 | High temperature solvent pretreatment method for improving yield of direct sodium-rich coal liquefaction oil |
| AU2017364656B2 (en) * | 2016-11-25 | 2020-07-30 | China University Of Mining And Technology | High temperature solvent pretreatment method for improving yield of direct sodium-rich coal liquefaction oil |
| CN113583756A (en) * | 2021-08-13 | 2021-11-02 | 北京化工大学 | Method for preparing chemicals and fuel oil by mild hydrogenation liquefaction of medium-low-rank coal |
| CN113583756B (en) * | 2021-08-13 | 2024-02-06 | 北京化工大学 | Method for preparing chemicals and fuel oil by mild hydrogenation liquefaction of medium-low rank coal |
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