CN102161904B - Method for increasing tar yield by coupling aromatization of hydrocarbons with coal pyrolysis - Google Patents
Method for increasing tar yield by coupling aromatization of hydrocarbons with coal pyrolysis Download PDFInfo
- Publication number
- CN102161904B CN102161904B CN 201110058218 CN201110058218A CN102161904B CN 102161904 B CN102161904 B CN 102161904B CN 201110058218 CN201110058218 CN 201110058218 CN 201110058218 A CN201110058218 A CN 201110058218A CN 102161904 B CN102161904 B CN 102161904B
- Authority
- CN
- China
- Prior art keywords
- coal
- pyrolysis
- aromatization
- hydrocarbons
- gas
- 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.)
- Active
Links
Images
Abstract
The utility model provides a method for increasing tar yield by coupling aromatization of hydrocarbons with coal pyrolysis. According to the method, hydrocarbon components taken as pyrolysis atmosphere are fed into a pyrolysis reactor through an inlet, activated by load-type metal catalysts and subjected to the aromatization, and then enter a coal pyrolysis layer for coupling pyrolysis with coal; and the reaction conditions are as follows: the temperature ranges from 300 DEG C to 1000 DEG C, the pressure ranges from 0.1 MPa to 3.0 MPa, the gas hourly space velocity ranges from 60 mL/g/h to 48000 mL/g/h, and the temperature is maintained constant for 0 minutes to 240 minutes. The method adopts hydrocarbons as the pyrolysis atmosphere instead of pure hydrogen gas for the pyrolysis, and increases the tar yield by coupling aromatization of hydrocarbons with coal pyrolysis. In the process, the cost of hydropyrolysis is reduced while the yield of tar is higher than the yield of tar produced by hydropyrolysis under the same conditions. Besides, the catalysts are not mixed with coal, and thus the catalysts are easy to be recycled and used repeatedly.
Description
Technical field
The invention belongs to energy technology field.Specifically relate to a kind of method of utilizing aromatization of hydrocarbons and pyrolysis of coal coupling to improve tar yield.
Background technology
In energy structure in China, coal is occupied an leading position.In the primary energy source production and consumption, coal accounts for 70%.The mode of utilizing of coal in China is mainly coking and generating at present, and because the reasons such as technical elements cause energy utilization rate lower, and environmental pollution is serious, and therefore clean coal transformation technology is imperative.Advanced coal transformation technology mainly contains pyrolytic technique, gasification technology, the liquefaction technology of coal, and the Poly-generation technology be coupled to form by these technology.Wherein, the pyrolysis of coal receives more and more investigators' concern with the diversity of its product and reaction conditions gentleness.The product liquid that pyrolysis of coal obtains, coal tar, be important industrial chemicals, contains a large amount of aromatic hydrocarbon and heterogeneous ring compound in tar, is the raw material of some special chemical preparations and new chemical materials.Yet traditional coal-tar middle oil productive rate of pyrolysis of coal process is lower.Although hydropyrolysis technique can improve tar yield, the hydrogen manufacturing cost is higher, restricts its application in industrial production.Therefore, developing new pyrolytic process replacement hydropyrolysis is a new research direction of coal pyrolysis technology.Up to the present, mainly contain following a few class in order to improve the pyrolytic process of coal that tar yield is purpose:
1. method for pretreating.By various pretreatment technology, can change to a certain extent the physics and chemistry structure of coal, thereby reach the purpose that improves tar yield.Cypres etc. utilize H
2, He, CO
2deng gas, coal sample is carried out to pre-treatment, wish to change the pore structure of coal to reach the purpose that improves tar yield.Found that, only have with hydrogen at 2～3MPa, 350～400 ℃ of pre-treatment coal samples, can improve to a certain extent tar yield, other several gas pre-treatment are to improving the pyrolytic tar productive rate without any effect (Cypres et al, Fuel Process, Technol, 1988,20:337).
2. catalytic pyrolysis method.Support the mode of transition-metal catalyst by original position, coal is carried out to pyrolysis, reach the purpose that improves tar yield.Kandiyoti etc. support ZnCl on coal sample
2, and carry out pyrolytic reaction under inert atmosphere.Found that, in the slow pyrolysis process, the char yeild obtained is higher, and tar yield reduces; On the contrary in the fast pyrogenation process, tar yield be greatly improved (Kandiyoti et al, Fuel, 1984,63,1583).
3. change the pyrolysis atmosphere method.By changing the reaction atmosphere in pyrolysis of coal, reach the purpose that improves tar yield.Chinese scholars has been made a large amount of research to this.Methane is high with its hydrogen-to-carbon ratio, wide material sources, and price is than the cheap concern that is subject to numerous researchers of hydrogen.Yet simple methane atmosphere carries out pyrolysis and inert atmosphere effect 500 ℃ of left and right, quite (Cypres et al, Fuel 1982,61:721-724).The research such as Smith finds that IBCSP No.5 coal is at CH
4-NO or CH
4-O
2pyrolysis under mixed atmosphere, the liquid product yield of gained higher than the productive rate under other atmosphere (Smith et al, Energy and Fuels, 1989,3:536-537).
4. Coupling Thermal solution.This is a kind of more concerned in recent years method that improves the pyrolytic tar productive rate.Be similar to the hydropyrolysis principle, additional free radical is provided in the process of pyrolysis of coal, make the free radical produced in the pyrolysis of coal process be stablized, reach the purpose that improves tar yield.Chinese patent ZL 200510045853.8 has invented the new pyrolytic process of a kind of methane portion oxidation and pyrolysis of coal coupling, at CH
4-CO
2under atmosphere, in the time of 750 ℃, the tar yield of Pingshuo Coal pyrolysis is than H under the same terms
2and N
2under atmosphere, improving a lot, (Liu et al, The 7
thchina-Korea Workshop on Clean Energy Technology, June 25-28,2008).
Summary of the invention
The purpose of this invention is to provide and a kind ofly take hydro carbons and replace traditional pure hydrogen atmosphere as reaction atmosphere, improve the method for tar yield by the mode of aromizing and pyrolysis of coal coupling.This technique can reduce the hydropyrolysis cost, and the gained tar yield is higher than the tar yield of hydropyrolysis under the same terms, and catalyzer is easy to cyclic regeneration, recycling.
For achieving the above object, the present invention adopts the method for aromatization of hydrocarbons and pyrolysis of coal coupling: take hydrocarbon component as pyrolytic reaction atmosphere, enter into pyrolysis reactor by entrance, after activating and aromatization occurs, load type metal catalyst enters the pyrolysis of coal responding layer, with the coal pyrolytic reaction that is coupled, its reaction conditions is: 300～1000 ℃ of temperature, pressure 0.1～3.0MPa, gas space velocity 60～48000mL/gh, constant temperature 0～240min, pyrogenous origin product is taken reactor out of with gas, by gas-liquid separator, collects tar products.
Described hydrocarbon component is Sweet natural gas, coal-seam gas, liquefied petroleum gas (LPG), single hydro carbons and be rich in any in the gas mixture of hydro carbons.
Described load type metal catalyst, comprise the metal catalyst that active ingredient is Cu, Ga, Ag, La, Zn, Ni, Fe, V, W, Mo, Re, Cr, Pt, Co etc., preferably Mo or Zn; Carrier is HZSM-5, HZSM-11, HZSM-8, HZRP-1, HMCM-22, HMCM-41, H β, HX, HY, HSAPO-34, HSAPO-5, HSAPO-11, Al
2o
3, SiO
2, MgO, ZrO
2in any, preferred HZSM-5.
Described pyrolysis reactor form is any in fixed bed and fluidized-bed.
Than prior art, the invention has the beneficial effects as follows: the hydro carbons of usining replaces pure hydrogen atmosphere to carry out pyrolysis as reaction atmosphere, and the mode be coupled by aromatization of hydrocarbons and pyrolysis of coal improves the pyrolysis of coal tar yield.This process, when reducing the hydropyrolysis cost, does not need the participation of oxygenant, and the productive rate of tar is higher than the tar yield of hydropyrolysis under the same terms, and catalyzer do not mix with coal, is easy to cyclic regeneration, reuses.
The accompanying drawing explanation
Fig. 1 is the structural representation of pyrolysis reactor in the present invention.
In figure, 1, catalyst layer, 2, coal seam, 3, gas distribution grid.
Embodiment
Comparative Examples 1
Selected coal is From Shenmu Coal, and its technical analysis and ultimate analysis are in Table one.Test coal 5g, catalyst-free, pyrolytical condition is 700 ℃ of temperature, constant temperature time 30min, pressure 0.1MPa, reaction gas is 25ml/minN
2, by gas inlet, enter reactor.Pyrogenous origin liquid product is taken reactor out of with gas, with cold-trap (20 ℃), collects.According to ASTM D95-83 method separating oil and water.The tar yield obtained thus is 14.6wt.%daf, and char yeild is 66.5wt.%daf.
Comparative Examples 2
Selected coal is From Shenmu Coal, and its technical analysis and ultimate analysis are in Table one.Test coal 5g, catalyst-free, pyrolytical condition is 700 ℃ of temperature, constant temperature time 30min, pressure 0.1MPa, reaction gas is 25ml/minH
2, by gas inlet, enter reactor.Pyrogenous origin liquid product is taken reactor out of with gas, with cold-trap (20 ℃), collects.According to ASTM D95-83 method separating oil and water.The tar yield obtained thus is 15.3wt.%daf, and char yeild is 66.1wt.%daf.
Comparative Examples 3
Selected coal is From Shenmu Coal, and its technical analysis and ultimate analysis are in Table one.Test coal 5g, catalyst-free, pyrolytical condition is 700 ℃ of temperature, constant temperature time 30min, pressure 0.1MPa, reaction gas is 25ml/minCH
4, by gas inlet, enter reactor.Pyrogenous origin liquid product is taken reactor out of with gas, with cold-trap (20 ℃), collects.According to ASTM D95-83 method separating oil and water.The tar yield obtained thus is 15.1wt.%daf, and char yeild is 66.7wt.%daf.
Selecting Mo/HZSM-5 is catalyzer, and its preparation method is: soak ammonium molybdate solution on the HZSM-5 powder, and room temperature dipping 16 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings 6 hours, through compression molding, filter out 20-40 order particle.
Selected coal is From Shenmu Coal, and its technical analysis and ultimate analysis are in Table one.Test coal 5g, catalyzer 1g, pyrolytical condition is 700 ℃ of temperature, constant temperature time 30min, pressure 0.1MPa, reaction gas is 25ml/minCH
4, by gas inlet, enter reactor.First after catalyst layer, enter coal seam, pyrogenous origin liquid product is taken reactor out of with gas again, with cold-trap (20 ℃), collects.According to ASTM D95-83 method separating oil and water.The tar yield obtained thus is 21.5wt.%daf, and char yeild is 65.6wt.%daf.
Selecting Mo/HZSM-5 is catalyzer, and its preparation method is: soak ammonium molybdate solution on the HZSM-5 powder, and room temperature dipping 16 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings 6 hours, through compression molding, filter out 20-40 order particle.
Selected coal is From Shenmu Coal, and its technical analysis and ultimate analysis are in Table one.Test coal 5g, catalyzer 1g, pyrolytical condition is 700 ℃ of temperature, constant temperature time 30min, pressure 0.1MPa, reaction gas is 60ml/minCH4, by gas inlet, enters reactor.First after catalyst layer, enter coal seam, pyrogenous origin liquid product is taken reactor out of with gas again, with cold-trap (20 ℃), collects.According to ASTM D95-83 method separating oil and water.The tar yield obtained thus is 19.0wt.%daf, and char yeild is 66.1wt.%daf.
Selecting Mo/HZSM-5 is catalyzer, and its preparation method is: soak ammonium molybdate solution on the HZSM-5 powder, and room temperature dipping 16 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings 6 hours, through compression molding, filter out 20-40 order particle.
Selected coal is From Shenmu Coal, and its technical analysis and ultimate analysis are in Table one.Test coal 5g, catalyzer 1g, pyrolytical condition is 750 ℃ of temperature, constant temperature time 30min, pressure 0.1MPa, reaction gas is 25ml/minCH4, by gas inlet, enters reactor.First after catalyst layer, enter coal seam, pyrogenous origin liquid product is taken reactor out of with gas again, with cold-trap (20 ℃), collects.According to ASTM D95-83 method separating oil and water.The tar yield obtained thus is 20.8wt.%daf, and char yeild is 64.9wt.%daf.
Embodiment 4
Selecting Zn/HZSM-5 is catalyzer, and its preparation method is: soak zinc nitrate solution on the HZSM-5 powder, and room temperature dipping 16 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings 2 hours, through compression molding, filter out 20-40 order particle.
Selected coal is From Shenmu Coal, and its technical analysis and ultimate analysis are in Table one.Test coal 5g, catalyzer 1g, pyrolytical condition is 500 ℃ of temperature, constant temperature time 30min, pressure 0.1MPa, reaction gas is 50ml/minC2H4, by gas inlet, enters reactor.First after catalyst layer, enter coal seam, pyrogenous origin liquid product is taken reactor out of with gas again, with cold-trap (20 ℃), collects.According to ASTM D95-83 method separating oil and water.The tar yield obtained thus is 23.0wt.%daf, and char yeild is 65.1wt.%daf.
Embodiment 5
Selecting Zn/HZSM-5 is catalyzer, and its preparation method is: soak zinc nitrate solution on the HZSM-5 powder, and room temperature dipping 16 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings 2 hours, through compression molding, filter out 20-40 order particle.
Selected coal is From Shenmu Coal, and its technical analysis and ultimate analysis are in Table one.Test coal 5g, catalyzer 1g, pyrolytical condition is 600 ℃ of temperature, constant temperature time 30min, pressure 0.1MPa, reaction gas is CH
4and C
2h
4gas mixture, its ratio of component 1: 1, the gas mixture flow velocity is 30ml/min, gas enters reactor by entrance.First after catalyst layer, enter coal seam, pyrogenous origin liquid product is taken reactor out of with gas again, with cold-trap (20 ℃), collects.According to ASTM D95-83 method separating oil and water.The tar yield obtained thus is 22.1wt.%daf, and char yeild is 65.3wt.%daf.
Table one From Shenmu Coal coal analysis data
Claims (2)
1. a method of utilizing aromatization of hydrocarbons and pyrolysis of coal coupling to improve tar yield, comprise the following steps: take hydrocarbon component as pyrolytic reaction atmosphere, enter into pyrolysis reactor by entrance, after activating and aromatization occurs, load type metal catalyst enters the pyrolysis of coal responding layer, with the coal pyrolytic reaction that is coupled, its reaction conditions is: 300～1000 ℃ of temperature, pressure 0.1～3.0MPa, gas space velocity 60～48000mL/gh, constant temperature 0～240min, pyrogenous origin product is taken reactor out of with gas, by gas-liquid separator, collects tar products;
Described hydrocarbon component is CH
4, or CH
4with C
2h
4gas mixture;
Described load type metal catalyst, its active ingredient is Mo or Zn; Carrier is HZSM-5.
2. a kind of method of utilizing aromatization of hydrocarbons and pyrolysis of coal coupling to improve tar yield according to claim 1, is characterized in that, described pyrolysis reactor form is any in fixed bed or fluidized-bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110058218 CN102161904B (en) | 2011-03-10 | 2011-03-10 | Method for increasing tar yield by coupling aromatization of hydrocarbons with coal pyrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110058218 CN102161904B (en) | 2011-03-10 | 2011-03-10 | Method for increasing tar yield by coupling aromatization of hydrocarbons with coal pyrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102161904A CN102161904A (en) | 2011-08-24 |
| CN102161904B true CN102161904B (en) | 2013-12-25 |
Family
ID=44463362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110058218 Active CN102161904B (en) | 2011-03-10 | 2011-03-10 | Method for increasing tar yield by coupling aromatization of hydrocarbons with coal pyrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102161904B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580726B (en) * | 2012-02-13 | 2015-08-05 | 北京神雾环境能源科技集团股份有限公司 | A kind of coal pyrolysis catalyst and method for making thereof |
| CN103571541B (en) * | 2012-07-30 | 2016-08-10 | 新奥科技发展有限公司 | A kind of co-production of methane and the catalysis gasification method of tar |
| CN103205268B (en) * | 2013-04-25 | 2014-11-26 | 新疆大学 | Low-order coal pyrolysis tar device and pyrolysis method of low-order coal pyrolysis tar |
| CN104293363A (en) * | 2014-10-24 | 2015-01-21 | 新疆大学 | Method and device for improving quality of coal pyrolytic tar by taking simulated pyrolysis gas as reaction atmosphere |
| CN112300818A (en) * | 2020-11-06 | 2021-02-02 | 赵海玲 | Method for preparing bio-oil by coupling biomass pyrolysis and methane aromatization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664069A (en) * | 2005-02-02 | 2005-09-07 | 大连理工大学 | Method for increasing tar yield of coalite pyrolysis with methane as reaction gas |
| CN101618337A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Method for improving catalytic property of methane aromatization catalyst |
| CN101747922A (en) * | 2010-01-05 | 2010-06-23 | 大连理工大学 | Method for increasing yield of coal-pyrolysis-based tar in reaction atmosphere of methane-rich gas mixture in fluidized bed |
-
2011
- 2011-03-10 CN CN 201110058218 patent/CN102161904B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664069A (en) * | 2005-02-02 | 2005-09-07 | 大连理工大学 | Method for increasing tar yield of coalite pyrolysis with methane as reaction gas |
| CN101618337A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Method for improving catalytic property of methane aromatization catalyst |
| CN101747922A (en) * | 2010-01-05 | 2010-06-23 | 大连理工大学 | Method for increasing yield of coal-pyrolysis-based tar in reaction atmosphere of methane-rich gas mixture in fluidized bed |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102161904A (en) | 2011-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Progress and prospects of hydrogen production: Opportunities and challenges | |
| CN102161904B (en) | Method for increasing tar yield by coupling aromatization of hydrocarbons with coal pyrolysis | |
| CN103289740B (en) | Method for preparing clean fuel oil from coal tar | |
| CN102974362B (en) | Catalyst for hydrogen production by catalytic reforming with biological oil and preparation method | |
| Wang et al. | Thermocatalytic hydrogenation of CO2 into aromatics by tailor‐made catalysts: Recent advancements and perspectives | |
| CN101654395A (en) | Process and method thereof for preparing lower alcohol by biomass | |
| CN101747922A (en) | Method for increasing yield of coal-pyrolysis-based tar in reaction atmosphere of methane-rich gas mixture in fluidized bed | |
| Mahmood et al. | Nanobiotechnology for the production of biofuels from spent tea | |
| CN102309967B (en) | Catalyst for hydrocarbon synthesis by CO2 catalytic hydrogenation and preparation method thereof | |
| CN103113187A (en) | Method for producing ethanol and coproducing ethyl acetate with acetic acid | |
| CN102701897A (en) | Method for preparing cyclic hydrocarbon compounds by hydrogenation of wash oil fraction | |
| CN110028983A (en) | A kind of method that biomass pyrolysis liquid hydrogenation deoxidation oil prepares aromatic hydrocarbons | |
| CN107233888B (en) | Multifunctional catalyst for preparing fuel gas from biomass and preparation method thereof | |
| CN113502174A (en) | Method for directly preparing aviation gasoline and aviation kerosene from polyolefin waste plastics | |
| CN102676219A (en) | Method for utilizing coal tar to produce gasoline and diesel | |
| CN113244923A (en) | Method for preparing carbon dioxide methanation reaction catalyst by using coal or biomass and application | |
| CN102876376A (en) | Method for improving hydrogenation production of gasoline and diesel oil by coal tar | |
| CN105647582A (en) | Method for synthesis of aviation kerosene cycloalkane and aromatic hydrocarbon components from bio-oil | |
| CN102863986A (en) | Coal tar hydrogenation upgrading method | |
| CN101564696A (en) | Reaction process and catalyst for preparing aromatic hydrocarbon by ethanol with one-step method | |
| CN102653393A (en) | Method for preparing hydrogen by utilizing waste biomass | |
| CN102070386A (en) | Two-step method for preparing olefin and aromatic hydrocarbon by catalyzing and upgrading bio-oil | |
| CN104788280A (en) | Method for preparing benzene toluene xylene (BTX) by aromatizing glycerinum | |
| CN106311339A (en) | Catalyst used for coal hydrogenation catalytic gasification, and preparation method and use thereof | |
| CN114574234A (en) | Production process of second-generation biodiesel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |