CN1477090A - Biomass indirect liquefaction one-step method for synthesizing dimethyl ether - Google Patents
Biomass indirect liquefaction one-step method for synthesizing dimethyl ether Download PDFInfo
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- 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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- gasification
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- dimethyl ether
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- 239000002028 Biomass Substances 0.000 title claims abstract description 39
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000007789 gas Substances 0.000 claims abstract description 48
- 238000002309 gasification Methods 0.000 claims abstract description 47
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 238000002407 reforming Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000011269 tar Substances 0.000 claims description 6
- 239000011285 coke tar Substances 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001833 catalytic reforming Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000004227 thermal cracking Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 239000003345 natural gas Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000003034 coal gas Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
本发明涉及生物质的高效洁净利用的一种新方法，进一步涉及利用沼气重整生物质气化气合成二甲醚的新方法。由于石油、煤和天然气等化石能源资源有限，从合成气制造燃料日益受到重视，生物质气化是生物质热转化技术中历史最长、最具实用性的一种技术。但生物质气化气与煤气化、天然气气化以及重渣油气化等途径获得的合成气相比，存在最大的弱点，即气化气中H2/CO值较低。目前二甲醚的合成主要通过煤气化、天然气气化以及重渣油气化等途径获得的合成气来合成。由生物质空气－水蒸汽催化气化产生的气化气经甲烷重整制备合成气直接合成洁净燃料二甲醚，是一种新的绿色合成工艺，至今未见报道。本发明提供一种完全由生物质高效清洁利用合成燃料二甲醚的绿色合成方法。The invention relates to a new method for high-efficiency and clean utilization of biomass, and further relates to a new method for synthesizing dimethyl ether by reforming biomass gasification gas with biogas. Due to the limited fossil energy resources such as oil, coal and natural gas, the production of fuel from syngas has been paid more and more attention. Biomass gasification is the longest and most practical technology among biomass thermal conversion technologies. However, compared with the synthesis gas obtained by coal gasification, natural gas gasification and heavy residue gasification, biomass gasification gas has the biggest weakness, that is, the H 2 /CO value in gasification gas is low. At present, DME is synthesized mainly through synthesis gas obtained from coal gasification, natural gas gasification and heavy residue gasification. The gasification gas produced by catalytic gasification of air-steam of biomass is reformed with methane to prepare syngas to directly synthesize clean fuel dimethyl ether, which is a new green synthesis process and has not been reported so far. The invention provides a green synthesis method for efficiently and cleanly utilizing biomass to synthesize fuel dimethyl ether.
Description
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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031265855A CN1477090A (en) | 2003-05-16 | 2003-05-16 | Biomass indirect liquefaction one-step method for synthesizing dimethyl ether |
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|---|---|---|---|
| CNA031265855A CN1477090A (en) | 2003-05-16 | 2003-05-16 | Biomass indirect liquefaction one-step method for synthesizing dimethyl ether |
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