CN103666549A - Method of separating liquid-solid product by direct coal liquefaction and circular solvent - Google Patents
Method of separating liquid-solid product by direct coal liquefaction and circular solvent Download PDFInfo
- Publication number
- CN103666549A CN103666549A CN201210359175.2A CN201210359175A CN103666549A CN 103666549 A CN103666549 A CN 103666549A CN 201210359175 A CN201210359175 A CN 201210359175A CN 103666549 A CN103666549 A CN 103666549A
- Authority
- CN
- China
- Prior art keywords
- liquid
- solid
- temperature
- coal liquefaction
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method of separating a liquid-solid product by direct coal liquefaction. The method comprises the following steps: A, heating the liquid-solid product after direct coal liquefaction to 30-200 DEG C and maintaining constant temperature; B, filter pressing the liquid-solid mixture in the step A to obtain filter residues and filtrate; and C, carrying out low temperature carbonization treatment on the filter residues in the step B to obtain low temperature carbonization oil and coke button. The invention further discloses a circular solvent. The method disclosed by the invention can increase the liquid-solid two-dimensional separation effect, improve the total yield of liquefied oil and reduce the energy consumption, and can be directly taken as the subsequent treatment program of a liquidation process, so that the benefit of the whole liquidation process is improved. The method is further suitable for coking coal oil mixtures such as coal tar and residual oil and liquid-solid separation.
Description
Technical field
The invention belongs to coal chemistry processing technique field, be specifically related to a kind of separation method of DCL/Direct coal liquefaction solid-liquid product, and the circulating solvent prepared of a kind of product obtaining via this separation method.
Background technology
Coal liquefaction be with coal be raw material, the liquid hydrocarbon of the take technology that is main products, be divided into " direct liquefaction " and " indirect liquefaction " two large classes: the direct liquefaction of (1) coal is that coal is under quite high temperature and pressure, catalytic hydrocracking generates liquid hydrocarbon and a small amount of carburet hydrogen, and removes the heteroatomic conversion processes such as nitrogen content of coal, oxygen and sulphur; (2) indirect liquefaction of coal is the synthetic gas (CO+H preparing with gasification
2) be raw material, under certain temperature and pressure, catalyze and synthesize the technique of hydrocarbon fuel oil and industrial chemicals.
Existing DCL/Direct coal liquefaction method has the advantages such as higher thermo-efficiency and liquid product yield, countries in the world have been dropped into a large amount of man power and materials and have been researched and developed, and form much relatively ripe technique, as, the IGOR technique of Germany, the NEDOL technique of Japan, the solvent refined coal process SRC of the U.S., H-coal process H-Coal, Exxon hydrogen donor solvent method EDS, catalysis two-stage hydrogenation liquefaction process CTSL, HTI technique and kerosene is sweetening process COP altogether, Muscovite low-voltage hydrogenation liquefaction process etc.And for example Chinese patent 200710032428.4 discloses a kind of thermally dissolving and catalytic method with brown coal preparing liquid fuel, the method comprises pulverized coal preparation step, coal slurry preparation process, thermally dissolving and catalytic step and thermosol liquefaction product separation step, its operational condition is gentle, can make the organic matter transformation rate in brown coal reach higher level, liquid feul can be prepared the motor spirit that meets national standard after processing; And Preparation equipment is simple, less investment, cost are low, is suitable for China's national situation.
The liquid-solid product of DCL/Direct coal liquefaction is a kind of containing the dregs of fat that highly filled, high pitch is rare and front pitch is rare, and the solid-liquid separation one of these dregs of fat is directly subordinate to world-famous puzzle.Early stage direct coal liquefaction process solid-liquid separation adopts filters, the old technique of Germany's World War II adopts centrifugal filtration process just, the filtrate that filtering separation obtains is contained more asphaltene and 2～12% solids, directly as circulating solvent, there is the poor problem of hydrogen supply capacity, cause reactive system operational difficulty, need to adopt the high pressure of 70MPa.At present, traditional solid-liquid separation process mainly contains underpressure distillation and solvent extraction etc.But underpressure distillation exists the problems such as circulating solvent lighting and coal liquefaction residue difficult treatment, solvent extraction is owing to will selecting suitable solvent, has many difficult problems such as the rotten and recovery of extraction solvent, therefore, is difficult to large-scale promotion always.
Summary of the invention
First object of the present invention is according to the deficiencies in the prior art part, and the separation method of the liquid-solid product of DCL/Direct coal liquefaction that a kind of technical process is simple, easy to operate, energy consumption is low and be easy to amplify is provided.
The circulating solvent that second object of the present invention is to provide a kind of product that utilizes above-mentioned separation method to prepare.
For reaching first object, the present invention adopts following technical scheme:
A separation method for the liquid-solid product of DCL/Direct coal liquefaction, comprises the steps:
A, the reacted liquid-solid product of DCL/Direct coal liquefaction is heated to 30～200 ℃ and constant temperature;
B, the liquid-solid mixture of A step is carried out to press filtration processing, obtain filter residue and filtrate;
C, the filter residue of B step is carried out to low-temperature pyrolysis processing, obtain low-temperature pyrolysis oil and cinder.
As preferably, the solid weight degree in the solid-liquid product of described A step is for being no less than 50%.
As preferably, the press filtration temperature of described B step is 30～200 ℃, press filtration pressure is 0.1～5.0Mpa, pressure atmosphere is vacuum or the inert atmosphere that adopts nitrogen or helium, press filtration filter cloth 500 order～1000 orders, filter cake thickness is controlled and is not more than 50mm, and time of filter pressing is 5～200min, and purges until filter cake is further dry with hot nitrogen.
As preferably, in C step, adopt continous way spiral heater to carry out low-temperature pyrolysis, the operational condition of described continous way spiral heater is: low-temperature pyrolysis temperature is 120～550 ℃, pressure is 0.02Mpa～0.3Mpa.
As preferably, described filtrate being contained 0.1%～0.02% solid, 10%～30% pitch is rare and front pitch is rare mink cell focus.
As preferably, described cinder is as the raw material of gasification and burning.
For reaching second object, the present invention adopts following technical scheme:
A circulating solvent, is to carry out after appropriate hydrogenation after filtrate that above-mentioned separation method is obtained and low-temperature pyrolysis oil mix, and obtains the hydrogenation circulating solvent for DCL/Direct coal liquefaction.
As preferably, the operational condition of described appropriate hydrogenation is: temperature of reaction is 240～380 ℃, and reaction pressure is 6～10Mpa, and reaction solution hourly space velocity LHSV is 0.3～1.5h
-1, vapour-liquid ratio is 300～1000m
3/ t; Hydrogenation catalyst chief component is: with two or more the active group member in Ni, Mo, Co, W element, one or both in Alpha-alumina, gama-alumina, silicon oxide and molecular sieve of take are carrier.
The present invention is by adopting technique scheme, the press filtration mink cell focus of usining can substitute out a large amount of light component in former solvent as the part of DCL/Direct coal liquefaction hydrogenation circulating solvent, increased liquid-solid two-phase separating effect, improved solvent degree of heaviness, can be directly as the postorder handling procedure of liquefaction process, greatly improve the overall liquid yield of gelatin liquefaction process, thereby improved the economic benefit of liquefaction factory.The present invention has that technical process is simple, easy to operate, energy consumption is low and be easy to the advantages such as amplification.The present invention is also applicable to coking and the solid-liquid separation of the coal oil mixtures such as coal tar, residual oil.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Now in conjunction with the accompanying drawings and embodiments the present invention is described in further detail:
Embodiment
The liquid-solid product of following embodiment is to adopt a kind of disclosed thermally dissolving and catalytic method with brown coal preparing liquid fuel of Chinese patent ZL200710032428.4 to obtain: will be through pulverizing dried coal dust (granularity 80～200 orders, moisture 2%～5%), the circulating solvent self generating and catalyst by proportion are fully uniformly mixed makes coal slurry, send into thermally dissolving and catalytic reactor, under the liquefaction condition of the method, carry out thermally dissolving and catalytic reaction, obtain liquid-solid product, the solid weight degree in this solid-liquid product is for being no less than 50%.
Embodiment 1
1, the separation of liquid-solid product
By the heat exchange to 160 ℃ of above-mentioned liquid-solid product, then enter surge tank constant temperature to 160 ℃ that the front band of pressure filter stirs.By liquid-solid product through the supercharging of slag stock pump, with 2000kg/h, enter filter-press (800 order filter cloth), under band pressure condition, make the suspended substance in slip constantly separated with liquid, in filtering unit chamber, save bit by bit and form gradually filter cake, and along with the rotation of rotary drum is sent filter-press; Filtrate is sent to solvent hydrogenation unit with 1400kg/h and carries out appropriate hydrogenation.Wherein: the filtrate obtaining being contained 0.1%～0.02% solid, 10%～30% pitch is rare and front pitch is rare mink cell focus; Press filtration condition is: press filtration temperature is 30～200 ℃, press filtration pressure is 0.1～5.0Mpa, pressure atmosphere is vacuum or the inert atmosphere that adopts nitrogen or helium, press filtration filter cloth 500 order～1000 orders, filter cake thickness is controlled and is not more than 50mm, time of filter pressing is 5～200min, and purges until filter cake is further dry with hot nitrogen.
The residue drawing off is sent to low-temperature pyrolysis unit (continous way spiral heater) with 600kg/h and carries out destructive distillation, gained empyreumatic oil is sent to solvent hydrogenation unit with 240kg/h and carries out appropriate hydrogenation, cinder is sent out-of-bounds with 360kg/h, as the raw material of gasification and burning.The operational condition of wherein said continous way spiral heater is: low-temperature pyrolysis temperature is 120～550 ℃, and pressure is 0.02Mpa～0.3Mpa.
2, the preparation of circulating solvent
Above-mentioned filtrate and empyreumatic oil carry out appropriate hydrogenation through being blended in solvent hydrogenation unit, obtain the hydrogenation circulating solvent for DCL/Direct coal liquefaction.Wherein the operational condition of appropriate hydrogenation is: temperature of reaction is 240～380 ℃, and reaction pressure is 6～10Mpa, and reaction solution hourly space velocity LHSV is 0.3～1.5h
-1, vapour-liquid ratio is 300～1000m
3/ t; Hydrogenation catalyst chief component is: with two or more the active group member in Ni, Mo, Co, W element, one or both in Alpha-alumina, gama-alumina, silicon oxide and molecular sieve of take are carrier.
Embodiment 2
1, the separation of liquid-solid product
By the liquid-solid product of room temperature through the supercharging of slag stock pump, with 2000kg/h, enter filter-press (800 order filter cloth), under band pressure condition, make the suspended substance in slip constantly separated with liquid, in filtering unit chamber, save bit by bit and form gradually filter cake, and along with the rotation of rotary drum is sent filter-press; Filtrate is sent to solvent hydrogenation unit with 1300kg/h and carries out appropriate hydrogenation.Wherein press filtration condition is: press filtration temperature is 30～200 ℃, press filtration pressure is 0.1～5.0Mpa, pressure atmosphere is vacuum or the inert atmosphere that adopts nitrogen or helium, press filtration filter cloth 500 order～1000 orders, filter cake thickness is controlled and is not more than 50mm, time of filter pressing is 5～200min, and purges until filter cake is further dry with hot nitrogen.Wherein: the filtrate obtaining being contained 0.1%～0.02% solid, 10%～30% pitch is rare and front pitch is rare mink cell focus
The residue drawing off is sent to continous way spiral heater with 700kg/h and carries out destructive distillation, and gained empyreumatic oil is sent to solvent hydrogenation unit with 340kg/h and carries out appropriate hydrogenation, and cinder is sent out-of-bounds with 360kg/h, as the raw material of gasification and burning.The operational condition of wherein said continous way spiral heater is: low-temperature pyrolysis temperature is 120～550 ℃, and pressure is 0.02Mpa～0.3Mpa.
2, the preparation of circulating solvent
Above-mentioned filtrate and empyreumatic oil carry out appropriate hydrogenation through being blended in solvent hydrogenation unit, obtain the hydrogenation circulating solvent for DCL/Direct coal liquefaction.Wherein the operational condition of appropriate hydrogenation is: temperature of reaction is 240～380 ℃, and reaction pressure is 6～10Mpa, and reaction solution hourly space velocity LHSV is 0.3～1.5h
-1, vapour-liquid ratio is 300～1000m
3/ t; Hydrogenation catalyst chief component is: with two or more the active group member in Ni, Mo, Co, W element, one or both in Alpha-alumina, gama-alumina, silicon oxide and molecular sieve of take are carrier.
Embodiment 3
1, the separation of liquid-solid product
By the heat exchange to 80 ℃ of above-mentioned liquid-solid product, then enter surge tank constant temperature to 80 ℃ that the front band of pressure filter stirs.To be preheated to the liquid-solid product of 80 ℃ through the supercharging of slag stock pump, with 2000kg/h, enter filter-press (1000 order filter cloth), under band pressure condition, make the suspended substance in slip constantly separated with liquid, in filtering unit chamber, save bit by bit and form gradually filter cake, and along with the rotation of rotary drum is sent filter-press; Filtrate is sent to solvent hydrogenation unit with 1320kg/h and carries out appropriate hydrogenation.Wherein: the filtrate obtaining being contained 0.1%～0.02% solid, 10%～30% pitch is rare and front pitch is rare mink cell focus; Press filtration condition is with embodiment 1.
The residue drawing off is sent to low-temperature pyrolysis unit with 680kg/h and carries out destructive distillation, and gained empyreumatic oil is sent to solvent hydrogenation unit with 320kg/h and carries out appropriate hydrogenation, and cinder is sent out-of-bounds with 360kg/h, as the raw material of gasification and burning.
2, the preparation of circulating solvent
Above-mentioned filtrate and empyreumatic oil carry out appropriate hydrogenation through being blended in solvent hydrogenation unit, obtain the hydrogenation circulating solvent for DCL/Direct coal liquefaction.Wherein the operational condition of appropriate hydrogenation is: temperature of reaction is 240～380 ℃, and reaction pressure is 6～10Mpa, and reaction solution hourly space velocity LHSV is 0.3～1.5h
-1, vapour-liquid ratio is 300～1000m
3/ t; Hydrogenation catalyst chief component is: with two or more the active group member in Ni, Mo, Co, W element, one or both in Alpha-alumina, gama-alumina, silicon oxide and molecular sieve of take are carrier.
Claims (8)
1. a separation method for the liquid-solid product of DCL/Direct coal liquefaction, is characterized in that, comprises the steps:
A, the reacted liquid-solid product of DCL/Direct coal liquefaction is heated to 30～200 ℃ and constant temperature;
B, the liquid-solid mixture of A step is carried out to press filtration processing, obtain filter residue and filtrate;
C, the filter residue of B step is carried out to low-temperature pyrolysis processing, obtain low-temperature pyrolysis oil and cinder.
2. separation method according to claim 1, is characterized in that, the solid weight degree in the solid-liquid product of described A step is for being no less than 50%.
3. separation method according to claim 1, it is characterized in that, the press filtration temperature of described B step is 30～200 ℃, press filtration pressure is 0.1～5.0Mpa, pressure atmosphere is vacuum or the inert atmosphere that adopts nitrogen or helium, press filtration filter cloth 500 order～1000 orders, and filter cake thickness is controlled and is not more than 50mm, time of filter pressing is 5～200min, and purges until filter cake is further dry with hot nitrogen.
4. separation method according to claim 1, it is characterized in that, in C step, adopt continous way spiral heater to carry out low-temperature pyrolysis, the operational condition of described continous way spiral heater is: low-temperature pyrolysis temperature is 120～550 ℃, and pressure is 0.02Mpa～0.3Mpa.
5. separation method according to claim 1, is characterized in that, described filtrate being contained 0.1%～0.02% solid, 10%～30% pitch is rare and front pitch is rare mink cell focus.
6. separation method according to claim 1, is characterized in that, described cinder is as the raw material of gasification and burning.
7. a circulating solvent, is characterized in that, after the filtrate that claim 1 is obtained and low-temperature pyrolysis oil mix, carries out after appropriate hydrogenation, obtains the hydrogenation circulating solvent for DCL/Direct coal liquefaction.
8. a kind of circulating solvent according to claim 7, is characterized in that, the operational condition of described appropriate hydrogenation is: temperature of reaction is 240～380 ℃, and reaction pressure is 6～10Mpa, and reaction solution hourly space velocity LHSV is 0.3～1.5h
-1, vapour-liquid ratio is 300～1000m
3/ t; Hydrogenation catalyst chief component is: with two or more the active group member in Ni, Mo, Co, W element, one or both in Alpha-alumina, gama-alumina, silicon oxide and molecular sieve of take are carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210359175.2A CN103666549A (en) | 2012-09-24 | 2012-09-24 | Method of separating liquid-solid product by direct coal liquefaction and circular solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210359175.2A CN103666549A (en) | 2012-09-24 | 2012-09-24 | Method of separating liquid-solid product by direct coal liquefaction and circular solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103666549A true CN103666549A (en) | 2014-03-26 |
Family
ID=50305332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210359175.2A Pending CN103666549A (en) | 2012-09-24 | 2012-09-24 | Method of separating liquid-solid product by direct coal liquefaction and circular solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103666549A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108368430A (en) * | 2015-12-21 | 2018-08-03 | 株式会社Posco | The manufacturing method and manufacturing device of coking additire |
| CN108977223A (en) * | 2018-07-25 | 2018-12-11 | 国家能源投资集团有限责任公司 | The preparation method and system of coal liquefaction circulation solvent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696252A (en) * | 2005-02-23 | 2005-11-16 | 刘玉忠 | Process method for recovering crude oil fallen to the ground |
| CN101182421A (en) * | 2007-12-13 | 2008-05-21 | 肇庆市顺鑫煤化工科技有限公司 | Thermally dissolving and catalytic method for preparing liquid fuel by lignite as well as catalyst and solvent used therefor |
| CN101962560A (en) * | 2010-09-29 | 2011-02-02 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN102010741A (en) * | 2010-11-26 | 2011-04-13 | 煤炭科学研究总院 | Method for directly liquefying coals with function of maximizing utilization of liquefied residues |
| CN102585895A (en) * | 2012-03-14 | 2012-07-18 | 李志英 | Separation method for solid particles in catalytic slurry oil |
-
2012
- 2012-09-24 CN CN201210359175.2A patent/CN103666549A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696252A (en) * | 2005-02-23 | 2005-11-16 | 刘玉忠 | Process method for recovering crude oil fallen to the ground |
| CN101182421A (en) * | 2007-12-13 | 2008-05-21 | 肇庆市顺鑫煤化工科技有限公司 | Thermally dissolving and catalytic method for preparing liquid fuel by lignite as well as catalyst and solvent used therefor |
| CN101962560A (en) * | 2010-09-29 | 2011-02-02 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN102010741A (en) * | 2010-11-26 | 2011-04-13 | 煤炭科学研究总院 | Method for directly liquefying coals with function of maximizing utilization of liquefied residues |
| CN102585895A (en) * | 2012-03-14 | 2012-07-18 | 李志英 | Separation method for solid particles in catalytic slurry oil |
Non-Patent Citations (1)
| Title |
|---|
| 李德飞等: ""煤液化残渣利用的研究进展"", 《广东化工》, vol. 39, no. 6, 25 June 2012 (2012-06-25), pages 137 - 138 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108368430A (en) * | 2015-12-21 | 2018-08-03 | 株式会社Posco | The manufacturing method and manufacturing device of coking additire |
| CN108977223A (en) * | 2018-07-25 | 2018-12-11 | 国家能源投资集团有限责任公司 | The preparation method and system of coal liquefaction circulation solvent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Feng et al. | Roles and fates of K and Ca species on biochar structure during in-situ tar H2O reforming over nascent biochar | |
| US9725653B2 (en) | Device and method for preparing oxygen-containing liquid fuel by bio-oil catalytic conversion | |
| CN102965131B (en) | Efficient and clean utilization technology for highly volatile young coal | |
| CN103275754B (en) | Method for separating liquefied heavy oil and asphalt substrate from direct coal liquefaction residues | |
| CN103265967B (en) | Method for preparing bio-oil by liquefying biomass by high efficiency hydro-thermal method | |
| CN102911691A (en) | Method for preparing bio-oil through supercritical pyrolysis of civil sludge | |
| CN105778968A (en) | Method for preparing impregnating pitch, impregnating pitch and application thereof | |
| CN102165049A (en) | Method for manufacturing hyper-coal | |
| CN102382683B (en) | Method for preparing biomass gas from plant branches and trunks | |
| CN103254933B (en) | Method for separating liquefied heavy oil and asphalt substances from direct coal liquefaction residues | |
| CN202924963U (en) | Processing system for preparing biological oil by municipal sludge supercritical pyrolysis method | |
| Elliott et al. | Production of liquid hydrocarbon fuels from peat | |
| CN107267186A (en) | The method that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon | |
| KR101515690B1 (en) | Method for reforming heavy hydrocarbon fraction and woody biomass | |
| CN113105915B (en) | Method and system for efficiently recovering heavy wax and catalyst in Fischer-Tropsch synthesis slag wax | |
| CN110540857A (en) | Method for preparing chemical raw material and liquid fuel from biomass | |
| CN103666549A (en) | Method of separating liquid-solid product by direct coal liquefaction and circular solvent | |
| CN102897714A (en) | Method for increasing yield of hydrogen in gas production process by using biomass | |
| CN116689456A (en) | Low-carbon recycling method for kitchen waste | |
| WO2020228488A1 (en) | Method for comprehensive utilization of biomass material | |
| CN103740393B (en) | Modifying asphalt, coal directly-liquefied residue is utilized to prepare method and the application thereof of modifying asphalt | |
| CN102504856A (en) | Method for preparing fuel oil by liquefying wood meal under normal pressure | |
| US20150051427A1 (en) | Integrated process for the production of renewable drop-in fuels | |
| CN109294612A (en) | A method of add hydrogen to prepare fuel oil altogether using sawdust and mink cell focus | |
| CN108315041A (en) | A kind of method of coal and biomass direct liquefaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140326 |