CN1477090A - Method for synthesizing dimethyl ether by adopting biomass indirect liquification one-step process - Google Patents

Method for synthesizing dimethyl ether by adopting biomass indirect liquification one-step process Download PDF

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Publication number
CN1477090A
CN1477090A CNA031265855A CN03126585A CN1477090A CN 1477090 A CN1477090 A CN 1477090A CN A031265855 A CNA031265855 A CN A031265855A CN 03126585 A CN03126585 A CN 03126585A CN 1477090 A CN1477090 A CN 1477090A
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biomass
dimethyl ether
gas
gasification
single stage
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CNA031265855A
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王铁军
常杰
吕鹏梅
祝京旭
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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Abstract

The present invention relates to a method for synthesizing dimethyl ether by high-effectively cleanly utilizing biomass. It utilizes the gasified gas produced by catalytic gasification of biomass air-water vapor, and makes the gasified gas undergo the process of methane reformation to prepare synthetic gas, and utilizes the synthetic gas to directly synthesize clean fuel dimethyl ether.

Description

The method of biomass indirect liquefaction single stage method dimethyl ether synthesis
Affiliated technical field:
The present invention relates to a kind of novel method of the efficient clean utilization of biomass, further relate to the novel method of utilizing biogas reforming biomass gasification gas dimethyl ether synthesis.
Technical background:
Will cause the exhaustion day by day of conventional energy resources in the future because fossil energy resource-constraineds such as oil, coal and Sweet natural gas, a large amount of exploitations use, make fuel from synthetic gas and come into one's own day by day.Dme is a kind of organic chemical industry's product and clean fuel that has development potentiality.Think after the U.S. relevant expert demonstration, dme be in the novel synthol of 21 century first choice of kind.Its main application is to make the propellent of aerosol and make industrial chemicals, substitutes diesel oil and makes domestic fuel as the automobile fuel and the replacement liquid liquefied oil gas of cleaning.Biomass are a kind of renewable energy sources, and reserves are very abundant, and the energy can be realized CO as an alternative 2Zero release, and S wherein, N content are low, alleviate Greenhouse effect and environmental pollution greatly.The efficient utilization of relevant biomass mainly concentrates on burning both at home and abroad, gasification utilizes the aspect, obtains combustible gas by gasification and comes combustion heat supplying or generating.
Gasifying biomass is a kind of technology of the longest, historical tool practicality in the biomass thermal transformation technology.But biomass gasified gas is compared with the synthetic gas that approach such as gasification, natural gas gasifying and heavy residual oil gasification obtain, and has maximum weakness, H in the gas that promptly gasifies 2/ CO value is lower, for improving the single-pass conversion efficient of biomass dimethyl ether synthesis, reduces must manage to improve the H of synthetic gas because of the carbon distribution inactivation of synthetic catalyst under poor hydrogen condition 2/ CO value.
The synthetic synthetic gas that mainly obtains by approach such as gasification, natural gas gasifying and heavy residual oil gasifications of dme synthesizes at present.The gasification gas that is produced by biomass air-water vapor catalytic gasification prepares the directly synthetic clean fuel dme of synthetic gas through methane reforming, is a kind of new green synthesis process, does not appear in the newspapers so far.The purpose of invention:
The objective of the invention is provides a kind of complete green synthesis method by biomass efficient clean utilization synthol dme for the Sustainable development that realizes the energy.
Summary of the invention:
A kind of method of biomass indirect liquefaction single stage method dimethyl ether synthesis comprises
Biomass enter fluidized-bed gasification furnace (2) through feeding screw (4), air is blown into by vapourizing furnace (2) bottom through sieve time blower fan, the high-temperature water vapor (400K) that steam generator (3) produces enters at the different heights of vapourizing furnace (2), and biomass are carried out air-water vapor catalytic gasification in vapourizing furnace (2);
The gasification gas that comes out from vapourizing furnace (2) enters coke tar cracking device (6) catalytic pyrolysis tar behind cyclonic separator (5) dedusting and coke, spray column (7) is to gasification gas deep purifying:
Gasification gas after the biogas that biogas generator (8) produces and the purification enters reforming reactor (10) catalytic reforming and produces synthetic gas after mixing tank (9) mixes;
Synthetic gas is synthetic after rectifier unit (12) separation and purification makes fuel dimethyl ether through dme synthesis reactor (11) catalysis.
Working gas of the present invention is air and water vapor, the catalyzer of catalytic gasification is homemade nickel-base catalyst in the vapourizing furnace, tar adopts catalytic thermal cracking method to purify, catalyzer is nickel/rhombspar dual-function catalyst, obtains hydrogen-rich gasification gas in the biomass fluidized bed gasification furnace behind air-water vapor catalytic gasification; Methane derives from the biogas that biomass produce.
The hydrogen rich gas gasification carries out catalytic reforming with the methane in the biogas and obtains H behind cyclonic separation, coke tar cracking and washing deep purifying 2: CO is 2: 1, and CO 2Content is less than 5% synthetic gas;
By one-step method from syngas synthol dme, behind separation and purification, be compressed into liquefied gas and use.
Description of drawings:
Fig. 1 is the device of biomass indirect liquefaction single stage method dimethyl ether synthesis.Among the figure, (1) sieve time blower fan; (2) fluidized-bed gasification furnace; (3) steam generator; (4) feeding screw; (5) cyclonic separator; (6) coke tar cracking device; (7) spray column; (8) biogas generator; (9) mixing tank; (10) reforming reactor; (11) single stage method synthesizer; (12) refining separation system.
Embodiment:
Biomass China fir powder enters fluidized-bed gasification furnace (2) by feeding screw (4), air is blown into by vapourizing furnace (2) bottom through sieve time blower fan, the high-temperature water vapor (400K) that steam generator (3) produces enters at the different heights of vapourizing furnace (2), biomass are carried out air-water vapor catalytic gasification in vapourizing furnace (2), H in the gasification gas 2: CO: CO 2: N 2It is 30: 10: 20: 30; The gasification gas that comes out from vapourizing furnace (2) enters coke tar cracking device (6) catalytic pyrolysis tar behind cyclonic separator (5) dedusting and coke, tar content is lower than 50mg/Nm 3, washing spray column (7) is to gasification gas deep purifying; After mixing tank (9) mixes, enter reforming reactor (10) catalytic reforming with gasification gas behind the marsh gas purifying that biogas generator (8) produces and produce synthetic gas, H in the synthetic gas 2: CO: CO 2: N 2It is 45: 25: 5: 20; Synthetic gas makes purity greater than 90% fuel dimethyl ether through synthetic after rectifier unit (12) separation and purification of single stage method synthesis reactor (11) catalysis, dme boil down to liquefied gas transportation and using.
The present invention has following outstanding advantages and good effect
1. in the reaction of biomass air-vapor catalytic gasification, take full advantage of the heat that the burning of part biological matter produces Provide gasification required heat, realize autothermal reaction;
2. produce the deficiency that a series of water gas shift reations overcome the living beings hydrogen content by adding water vapour, reach Improve the purpose of the potential hydrogen output of living beings;
3. in the reaction of biomass air-vapor catalytic gasification, utilize homemade nickel-base catalyst to realize significantly carrying The purpose of the potential hydrogen output of high living beings;
4. the methane reforming that is provided by biogas is provided in the reformation operation of hydrogen rich gas gas, makes whole synthesis technique complete Section adopts reproducible biomass resource, has realized green synthesis route;
5. in the methane reforming operation, realize adjustment synthesis gas ratio by homemade reforming catalyst, reduced CO2The purpose of content.

Claims (6)

1, a kind of method of biomass indirect liquefaction single stage method dimethyl ether synthesis comprises following process:
Biomass starting material enters fluidized-bed gasification furnace (2) through feeding screw (4), air is blown into by vapourizing furnace (2) bottom through sieve time blower fan, the high-temperature water vapor (400K) that steam generator (3) produces enters at the different heights of vapourizing furnace (2), and biomass are carried out air-water vapor catalytic gasification in vapourizing furnace (2);
The gasification gas that comes out from vapourizing furnace (2) enters coke tar cracking device (6) catalytic pyrolysis tar behind cyclonic separator (5) dedusting and coke, spray column (7) is to gasification gas deep purifying;
Gasification gas after the biogas that biogas generator (8) produces and the purification enters reforming reactor (10) catalytic reforming and produces synthetic gas after mixing tank (9) mixes;
Synthetic gas is synthetic after rectifier unit (12) separation and purification makes fuel dimethyl ether through dme synthesis reactor (11) catalysis.
2, the method for a kind of biomass indirect liquefaction single stage method dimethyl ether synthesis according to claim 1 is characterized in that working gas is air and water vapor.
3, the method for a kind of biomass indirect liquefaction single stage method dimethyl ether synthesis according to claim 1, the catalyzer that it is characterized in that air and water vapor catalytic gasification is homemade nickel-base catalyst.
4, the method for a kind of biomass indirect liquefaction single stage method dimethyl ether synthesis according to claim 1, the tar in the gas that it is characterized in that gasifying adopt catalytic thermal cracking method to purify, and catalyzer is nickel/rhombspar dual-function catalyst.
5, the method for a kind of biomass indirect liquefaction single stage method dimethyl ether synthesis according to claim 1 is characterized in that mending hydrogen and the adjustment of synthetic gas ratio by the water vapor and the CO 2 reformation of methane; The ratio of synthetic gas is: H 2: CO is 2: 1, and CO 2Content is less than 5%.
6, a kind of according to claim 1 or 5 method of biomass indirect liquefaction single stage method dimethyl ether synthesis is characterized in that described methane derives from the biogas that biomass produce.
CNA031265855A 2003-05-16 2003-05-16 Method for synthesizing dimethyl ether by adopting biomass indirect liquification one-step process Pending CN1477090A (en)

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CN101033427B (en) * 2007-04-04 2010-06-23 苏宏文 Dimethyl ether prepared from marsh gas and preparing method for the same
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US7897126B2 (en) 2007-12-28 2011-03-01 Greatpoint Energy, Inc. Catalytic gasification process with recovery of alkali metal from char
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US8088832B2 (en) 2006-04-05 2012-01-03 Woodland Biofuels Inc. System and method for converting biomass to ethanol via syngas
US8114177B2 (en) 2008-02-29 2012-02-14 Greatpoint Energy, Inc. Co-feed of biomass as source of makeup catalysts for catalytic coal gasification
US8114176B2 (en) 2005-10-12 2012-02-14 Great Point Energy, Inc. Catalytic steam gasification of petroleum coke to methane
US8123827B2 (en) 2007-12-28 2012-02-28 Greatpoint Energy, Inc. Processes for making syngas-derived products
US8163048B2 (en) 2007-08-02 2012-04-24 Greatpoint Energy, Inc. Catalyst-loaded coal compositions, methods of making and use
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US8202913B2 (en) 2008-10-23 2012-06-19 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
CN102597182A (en) * 2009-08-04 2012-07-18 Sk新技术株式会社 Method for gasification of carbon-containing materials by thermal decomposition of methane and conversion of carbon dioxide
US8268899B2 (en) 2009-05-13 2012-09-18 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
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US8286901B2 (en) 2008-02-29 2012-10-16 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US8297542B2 (en) 2008-02-29 2012-10-30 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US8328890B2 (en) 2008-09-19 2012-12-11 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
US8349039B2 (en) 2008-02-29 2013-01-08 Greatpoint Energy, Inc. Carbonaceous fines recycle
US8361428B2 (en) 2008-02-29 2013-01-29 Greatpoint Energy, Inc. Reduced carbon footprint steam generation processes
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US8557878B2 (en) 2010-04-26 2013-10-15 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with vanadium recovery
US8648121B2 (en) 2011-02-23 2014-02-11 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with nickel recovery
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US8652222B2 (en) 2008-02-29 2014-02-18 Greatpoint Energy, Inc. Biomass compositions for catalytic gasification
US8652696B2 (en) 2010-03-08 2014-02-18 Greatpoint Energy, Inc. Integrated hydromethanation fuel cell power generation
US8653149B2 (en) 2010-05-28 2014-02-18 Greatpoint Energy, Inc. Conversion of liquid heavy hydrocarbon feedstocks to gaseous products
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US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea

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