CN101230296A - Reforming reactor and method for preparing synthetic gas by biomass raw fuel gas - Google Patents
Reforming reactor and method for preparing synthetic gas by biomass raw fuel gas Download PDFInfo
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- CN101230296A CN101230296A CNA2007100328887A CN200710032888A CN101230296A CN 101230296 A CN101230296 A CN 101230296A CN A2007100328887 A CNA2007100328887 A CN A2007100328887A CN 200710032888 A CN200710032888 A CN 200710032888A CN 101230296 A CN101230296 A CN 101230296A
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Abstract
The invention discloses a reforming reactor and a method, which uses biomass rough fuel gas to prepare synthesis gas. The method include the following steps that a great mass of coke particles in high-temperature rough fuel gas which is produced by gasifying the biomass are removed after undergoing cyclone separation; and then the high-temperature rough fuel gas is sent into the reforming reactor; simultaneously overheated vapor and oxygen are added into the reforming reactor, the high-temperature rough fuel gas undergoes oxygen contacting catalytic reforming under the action of catalyst in the reforming reactor and at a reaction temperature of between 640 DEG C and 850 DEG C, and the high-temperature rough fuel gas is directively transformed into synthesis gas which mainly contains H2, CO and CO2 constituents. The reformed synthesis gas enters into a synthesis system after undergoing cooling and dust removing. The invention applies the oxygen contacting reaction technology to prepare high-grade synthetic gas in the catalytic reforming process of the biomass rough fuel gas; can save energy, lower consumption, and reduce emission greatly; can prolong the regeneration cycle and service life of the catalyst. The invention realizes integrated sustainable utilization of biomass resource, energy and environment.
Description
Technical field
The invention provides a kind of high effect cleaning and produce the technology and the method for higher-grade biosynthesizing gas, particularly a kind of reforming reactor of preparing synthetic gas by biomass raw fuel gas and method.
Technical background
China is the poor relatively country of hydrocarbon resources, and rising steadily of international oil price produced material impact to China's economy in recent years, and the energy security and the national security of China have also been brought sizable pressure.Biomass are unique carbon resources that can be converted into liquid fuel in the renewable energy source, biomass synthesis gas production technology by developing low-cost, with the depleted biomass resource is the synthetic high-quality liquid fuel of raw material, for realizing that China's energy structure diversification, enhancing energy security have great importance.
Based on the energy exploitation and application discharging of fossil oil a large amount of greenhouse gases, toxic and harmful and waste residue, waste water, waste oil etc., be the major cause that causes environmental pollution and climate change.Along with adding Kyoto Protocol CO formally fulfils in China
2Duties of cutting emissions, the CO of China
2Reduce discharging pressure with increasing.Therefore biomass synthetic liquid fuel production process environmental friendliness, develops the biomass synthetic fuel industry on a large scale, can reduce CO significantly
2Discharging, be fundamentally to solve the mineral substance energy expenditure to cause one of effective way of topsoil and Greenhouse effect, help the protection of ecotope, realize social sustainable development.
At present, countries in the world are just being used for reference the achievement and the experience of syngas production from NG industry at present, on more sophisticated gasifying biomass engineering basis, extensively carry out the research and development that biogas reformation modulation is produced synthetic gas, to satisfy the requirement of downstream liquid fuel synthesis system.Because biomass coke tar is mainly the very complicated fused ring compound of composition, reforming process causes the nickel-base catalyst coking deactivation easily, and it is high to make that biomass rough gas purifies with component reformation modulation cost.
Face the oxygen reaction technology in the pyroreaction of many easy carbon deposits, be proved to be and eliminate the highly effective method of catalyst surface carbon deposit, in industrial production technology, be widely adopted gradually in recent years.
Summary of the invention
One of purpose of the present invention provides the method that the high quality synthetic gas is produced in a kind of thick combustion gas, solves catalyst surface carbon distribution coking in the reforming process and causes catalytic activity to descend the degradation problem rapidly.
For achieving the above object, the present invention has taked following technical scheme:
A kind of method of preparing synthetic gas by biomass raw fuel gas comprises the steps:
(1) the biomass thick combustion gas of high temperature that obtains of gasifying is removed most of coke granule through cyclonic separation;
(2) send into reforming reactor again; In reforming reactor, add overheated steam and oxygen simultaneously, wherein, the thick combustion gas and the O of adding
2Mol ratio be 100: 2～6, the amount that adds water vapour in every cubic metre of thick combustion gas is 0.12～1.20kg/m
3Face the oxygen catalytic reforming under the catalyst action of the thick combustion gas of high temperature in reforming reactor, orientation is converted into and mainly contains H
2, CO and CO
2The synthetic gas of component; Described catalyzer is high steady nickel magnesium sosoloid catalyzer; Face oxygen catalytic reforming reaction temperature between 640～850 ℃;
(3) synthetic gas that makes after the reformation enters synthesis system then after cooling, dedusting.
Described preparation method also comprises the steps:
Before facing the oxygen catalytic reforming, between 700～850 ℃ of temperature with reforming catalyst reduction activation 1～3 hour.
Preferably, the thick combustion gas and the O of the adding in the above-mentioned steps (2)
2Mol ratio be 100: 3, the amount of water vapour is 0.8～1kg/m
3Temperature of reaction is 700～800 ℃.
Preferably, the steady nickel magnesium sosoloid of described height catalyzer is prepared by following method:
(1) with Ni (AC)
2, Mg (NO3)
2Crystal is dissolved in the distilled water, is made into Ni, Mg atomic molar ratio and is 2: 100～5: 100 solution a.
(2) earlier mixed solution a is heated to 57-62 ℃, uses isopyknic 2mol/L K again
2CO
3Solution titration in beaker under agitation keeps solution constant temperature at 57 ℃ simultaneously, and dripping periodic rate of titration is 10-15ml/min, and the pH value remains between the 8-10;
(3) leave standstill 1.5-2.5 hour after, suction filtration, and use 60 ℃ of hot water injections is rapidly used (the NH of a large amount of 0.1mol/l then
4) HCO
3K is removed in the solution flushing
+
(4) under 120 ℃, carry out drying 12 hours, calcine congruent melting 20 hours down at 950 ℃ then, last extrusion molding.
Another object of the present invention provides the reforming reactor of the method that is used for above-mentioned preparing synthetic gas by biomass raw fuel gas.
The technical scheme that realizes this purpose is as follows: a kind of reforming reactor, in reactor, be provided with upper spacer, lower clapboard and the space in the reactor is divided into exhaust chest, smoke chamber, dust collection chamber from top to bottom, be provided with at least two reaction tubess in smoke chamber, the two ends of this reaction tubes are run through upper spacer, lower clapboard respectively; Be provided with filter screen in the lower port position of reaction tubes and in the pipe of reaction tubes space and dust collection chamber be separated by; On the wall of reactor, be provided with gas supplementing opening, thick fuel gas inlet, smoke inlet, exhanst gas outlet, reformation gas outlet; Dust collection chamber top communicates with the external world respectively by gas supplementing opening, thick fuel gas inlet, and smoke chamber bottom, smoke chamber top communicate with the external world respectively by smoke inlet, exhanst gas outlet respectively, and exhaust chest communicates with the external world by the reformation gas outlet.
Preferably, described gas supplementing opening includes oxygen inlet, water vapour import.The bottom of described reforming reactor is provided with ash output hole, and described dust collection chamber communicates with the external world by this ash output hole.
The present invention will face the catforming process that the oxygen reaction technology is applied to biogas, the CH in the biogas
4, C
2, C
3And tar optionally is converted into H
2And CO, and remarkable modulation H
2/ CO ratio prolongs the regeneration period and the work-ing life of catalyzer greatly, further improves the long-term operation stability of biomass synthesis gas gasification system, reduces catalyst consumption and system maintenance cost, will become one of important directions of advanced reforming process research and development.
The present invention will face the catforming process that the oxygen reaction technology is applied to biomass rough gas and prepare the higher-grade synthetic gas, and significantly saving energy, lowering energy consumption and reducing pollutants discharge prolong the regeneration period and the work-ing life of catalyzer.Realized the integrated sustainability utilization of biomass resource-energy-environment.
Description of drawings
Fig. 1 is the equipment synoptic diagram used in the method for synthetic gas for preparing of the present invention;
Fig. 2 is among Fig. 1, the structural representation of reforming reactor;
Fig. 3 is among Fig. 2, the A-A sectional view;
The explanation of accompanying drawing sign
1, biomass feed system, 2, fluidized-bed gasification furnace, 3, cyclonic separator, 4, Pintsch process device, 5, the coke feed device, 6, burner, 7, reforming reactor, 8, reforming reactor dust collection chamber, 9, smoke chamber 10, reaction tubes, 11, ash output hole, 12, metal filter screen, 13, smoke inlet, 14, thick fuel gas inlet, 15, exhanst gas outlet, 16, reformation gas outlet, 17, heat exchanger, 18, sack cleaner, 19, the pulse backblowing device, 20, exhaust chest, 21, upper spacer, 22, lower clapboard, G1, vapourizing furnace O
2Import G2, vapourizing furnace water vapour import G3, O
2Import G4, water vapour import.
Embodiment
In following examples, will further specify the present invention, but the present invention will not be construed as limiting.
One: Preparation of catalysts
The high steady nickel magnesium sosoloid catalyzer of preparation as follows:
(1) with Ni (AC) 2, Mg (NO
3)
2Crystal is dissolved in the distilled water, is made into Ni, Mg atomic molar ratio and is 3.3: 100 solution a.
The K that joins 2mol/L
2CO
3Solution, (the NH of 0.1mol/L
4) HCO
3Solution.
(2) earlier mixed solution a is heated to 57+5 ℃, uses isopyknic K again
2CO
3Solution titration in beaker under agitation keeps solution constant temperature at 330K (57 ℃) simultaneously, controls rate of titration during titration well, generally is controlled at 10-15ml/min, and the pH value remains in the 8-10.
(3) leave standstill two hours after, suction filtration, and use 60 ℃ of hot water injections is rapidly used (the NH of a large amount of 0.1mol/l then
4) HCO
3K is removed in the solution flushing
+
(4) under 120 ℃, carry out drying 12 hours, calcine congruent melting 20 hours down at 1223K (950 ℃) then.Last extrusion molding.And add in the reaction tubes that is contained in reforming reactor.
Two. reforming reactor
As shown in Figure 1-Figure 3, the equipment of the preparing synthetic gas by biomass raw fuel gas of present embodiment is mainly by biomass feed system 1, fluidized-bed gasification furnace 2, cyclonic separator 3, Pintsch process device 4, coke feed device 5, burner 6, reforming reactor 7, heat exchanger 17, sack cleaner 18, pulse backblowing device 19 and vapourizing furnace oxygen and water vapour import G1 and G2.Its reforming reactor 7 is a shell and tube reactor, in reactor, be provided with upper spacer 21, lower clapboard 22 and the space in the reactor is divided into exhaust chest 20, smoke chamber 9, dust collection chamber 8 from top to bottom, be provided with 12 reaction tubess 10 (as shown in Figure 3) in smoke chamber 9, the two ends of this reaction tubes 10 are run through upper spacer 21, lower clapboard 22 respectively and are communicated with exhaust chest 20, dust collection chamber 8; Be provided with metal filter screen 12 in the lower port position of reaction tubes 10 and in the pipe of reaction tubes 10 space and dust collection chamber 8 be separated by; On the wall of reactor, be provided with O
2Import G3, water vapour import G4, thick fuel gas inlet 14, smoke inlet 13, exhanst gas outlet 15, reformation gas outlet 16; Dust collection chamber passes through O in 8 tops
2Import G3, water vapour import G4 respectively with O
2Inlet pipe, water vapour inlet pipe communicate, dust collection chamber 8 tops communicate with thick gas inlet pipe by thick fuel gas inlet 14, smoke chamber 9 bottoms by smoke inlet 13 communicate with smoke inlet pipe, smoke chamber 9 tops communicate with the flue gas escape pipe by exhanst gas outlet 15, exhaust chest 20 goes out pipe by reformation gas outlet 16 with the reformation combustion gas and communicates.Ash output hole 11 is arranged on the bottom of reforming reactor 7, and described dust collection chamber 8 communicates with the external world by this ash output hole 11.
Three. preparing synthetic gas by biomass raw fuel gas
Biomass material enters vapourizing furnace 2 through feed system 1, and igniting driving aerogenesis, high-temperature fuel gas are directly sent into burner 6 burnings after cyclonic separation is removed most of coke granule, and the high-temperature flue gas of generation carries out heat temperature raising to reforming reactor 7 and Pintsch process device 4.After 780 ℃ of the reforming reaction temperature of waiting to reach predetermined, open Pintsch process device feed system, biomass material is decomposed into coke and fugitive constituent (combustion gas and oil vapour) through Pintsch process, coke is sent into vapourizing furnace 2 gasifications by coke feed device 5, fugitive constituent is sent into burner 6 burnings, and the heat of generation is supplied with reforming reactor 7; The high-temperature fuel gas that progressively vapourizing furnace is produced switches to reforming reactor reaction tubes 10 simultaneously, and reforming catalyst was carried out reduction activation 2 hours, and reduction temperature is 780 ℃.
After the reforming catalyst reduction activation is finished, adding mol ratio with the thick combustion gas of high temperature from oxygen intake G3 to the biomass high-temperature gas-flow is 100: 3 oxygen, add overheated steam from steam entry G4, the water vapour add-on is 0.8kg in every cubic metre of thick combustion gas.Under the effect of catalyzer, the thick combustion gas of high temperature reacts at reaction tubes 10,780 ℃ of temperature of reaction, the CH in the thick combustion gas
4, C
2, C
3And tar optionally is converted into H
2And CO, the high temperature gas flow of discharging from catalytic bed enters sack cleaner 18 after waste heat boiler 17 heat exchange cooling, send into follow-up synthesis system then after supercharging.The synthesis purge gas of synthesis system stops up to prevent catalytic bed through pulse blowback device 19 timing blowback reaction tubess 10 and sack cleaner 18, and the dust ash content that the reforming reactor blowback is got off is collected in reforming reactor dust collection chamber 8, regularly removes from ash output hole 11.
The catalytic reforming reaction system moves 300 hours continuously under these conditions, and catalyzer does not detect the carbon distribution inactivation, to the analysis revealed of gas composition after the reforming reaction, H
2/ CO ratio is 1.3, the CH in the synthetic gas
4Content is reduced to below the 0.2mol%, and the tar transformation efficiency in the biomass rough gas reaches more than 99%, and tar content is lower than 0.1mg/m
3Traditional back of reforming is as shown in table 1 with the whole coal-tar middle oil component of oxygen reformation back synthetic gas of facing.
Table 1 is non-to face oxygen reform back and the whole oxygen coal-tar middle oil component of back synthetic gas of reforming of facing
| Residual hydro carbons | The non-oxygen that faces weighs | It is heavy to face oxygen | Residual hydro carbons | The non-oxygen that faces weighs | It is heavy to face oxygen |
| 1-butylene | 10.30 | 8.32 | Toluene | 298.78 | 82.1 |
| Trans-2-butene | 0 | 0 | Ethylbenzene | 33.31 | 0 |
| Cis-butene | 0 | 0 | Between, right-dimethylbenzene | 66.06 | 0 |
| Butane | 0 | 0 | Vinylbenzene | 332.98 | 0 |
| The 3-methyl isophthalic acid- | 6.52 | 0 | Ortho-xylene | 38.41 | 0 |
| The 1-amylene | 11.05 | 0 | The 2-methylphenol | 34.83 | 0 |
| The 2-methyl isophthalic acid- | 4.58 | 0 | Phenol | 19.22 | 0 |
| Isoprene | 8.83 | 0 | 1, the 3-cyclopentenes | 32.26 | 0 |
| Cis-2-amylene | 4.09 | 0 | Methyl-isobutyl ether | 12.95 | 0 |
| Cyclopentenes | 2.69 | 0 | Carbonylsulfide | 0 | 0 |
| 2-methyl-2- | 0 | 0 | Naphthalene | 0 | 0 |
| Benzene | 776.11 | 512.71 | Methane | 4mol％ | 0.2mol％ |
Catalyst system therefor is identical with embodiment 1.
Used cat reformer and preparation method are basic identical, and that difference is is thick combustion gas and the O that adds
2Mol ratio be 100: 2, the amount of water vapour is 0.2kg/m
3Under the catalyst action of the thick combustion gas of high temperature in reforming reactor, in temperature of reaction is 780 ℃.
The catalytic reforming reaction system moves 300 hours continuously under these conditions, and catalyzer does not detect the carbon distribution inactivation, to the analysis revealed of gas composition after the reforming reaction, H
2/ CO ratio is 1.02, and the CH4 content in the synthetic gas is reduced to below the 0.3mol%, and the tar transformation efficiency in the biomass rough gas reaches more than 99%, and tar content is lower than 0.1mg/m
3
Catalyst system therefor is identical with embodiment 1.
Used cat reformer and preparation method are basic identical, and that difference is is thick combustion gas and the O that adds
2Mol ratio be 100: 5, the amount of water vapour is 1.2kg/m
3Under the catalyst action of the thick combustion gas of high temperature in reforming reactor, in temperature of reaction is 780 ℃.
The catalytic reforming reaction system moves 300 hours continuously under these conditions, and catalyzer does not detect the carbon distribution inactivation, to the analysis revealed of gas composition after the reforming reaction, H
2/ CO ratio is 1.3, and the CH4 content in the synthetic gas is reduced to below the 0.1mol%, and the tar transformation efficiency in the biomass rough gas reaches more than 99%, and tar content is lower than 0.1mg/m
3
Claims (7)
1. the method for a preparing synthetic gas by biomass raw fuel gas is characterized in that, comprises the steps:
(1) the biomass thick combustion gas of high temperature that obtains of gasifying is removed most of coke granule through cyclonic separation;
(2) send into reforming reactor again; In reforming reactor, add overheated steam and oxygen simultaneously, wherein, the thick combustion gas and the O of adding
2Mol ratio be 100: 2～6, the add-on 0.12～1.20kg of water vapour in every cubic metre of thick combustion gas; Under the catalyst action of the thick combustion gas of high temperature in reforming reactor, in temperature of reaction is to face the oxygen catalytic reforming between 640～850 ℃, and orientation is converted into and mainly contains H
2, CO and CO
2The synthetic gas of component; Described catalyzer is high steady nickel magnesium sosoloid catalyzer;
(3) synthetic gas after the reformation enters synthesis system then after cooling, dedusting.
2. the method for preparing synthetic gas by biomass raw fuel gas according to claim 1 is characterized in that, also comprised the steps: before facing the oxygen catalytic reforming, between 700～850 ℃ of temperature with reforming catalyst reduction activation 1～3 hour.
3. the method for preparing synthetic gas by biomass raw fuel gas according to claim 1 is characterized in that, the thick combustion gas and the O of the adding in the step (2)
2Mol ratio be 100: 3, the amount that adds water vapour in every cubic metre of thick combustion gas is 0.8～1.20kg; Temperature of reaction is 700～800 ℃.
4. according to each described preparing synthetic gas by biomass raw fuel gas method of claim 1-3, it is characterized in that: the steady nickel magnesium sosoloid of described height catalyzer is prepared by following method:
(1) with Ni (AC)
2, Mg (NO3)
2Crystal is dissolved in the distilled water, is made into Ni, Mg atomic molar ratio and is 2: 100～5: 100 solution a;
(2) earlier mixed solution a is heated to 57-62 ℃, uses isopyknic 2mol/L K again
2CO
3Solution titration in beaker under agitation keeps solution constant temperature at 57 ℃ simultaneously, and dripping periodic rate of titration is 10-15ml/min, and the pH value remains between the 8-10;
(3) leave standstill 1.5-2.5 hour after, suction filtration, and use 60 ℃ of hot water injections is rapidly used (the NH of a large amount of 0.1mol/l then
4) HCO
3K is removed in the solution flushing
+
(4) under 120 ℃, carry out drying 12 hours, calcine congruent melting 20 hours down at 950 ℃ then, last extrusion molding.
5. reforming reactor that is used for the described preparing synthetic gas by biomass raw fuel gas method of claim 1, it is characterized in that: in reactor, be provided with upper spacer (21), lower clapboard (22) and the space in the reactor is divided into exhaust chest (20), smoke chamber (9), dust collection chamber (8) from top to bottom, be provided with at least two reaction tubess (10) in smoke chamber (9), the two ends of this reaction tubes (10) are run through upper spacer (21), lower clapboard (22) respectively; Be provided with filter screen (12) in the lower port position of reaction tubes (10) and in the pipe of reaction tubes (10) space and dust collection chamber (8) be separated by; On the wall of reactor, be provided with gas supplementing opening, thick fuel gas inlet (14), smoke inlet (13), exhanst gas outlet (15), reformation gas outlet (16); Dust collection chamber (8) top communicates with the external world respectively by gas supplementing opening, thick fuel gas inlet (14), smoke chamber (9) bottom, smoke chamber (9) top communicate with the external world respectively by smoke inlet (13), exhanst gas outlet (15) respectively, and exhaust chest (20) communicates with the external world by reformation gas outlet (16).
6. reforming reactor according to claim 5 is characterized in that, described gas supplementing opening includes oxygen inlet (G3), water vapour import (G4).
7. reforming reactor according to claim 5 is characterized in that, the bottom of described reactor is provided with ash output hole (11), and described dust collection chamber (8) communicates with the external world by this ash output hole (11).
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102124083A (en) * | 2008-08-15 | 2011-07-13 | 科诺科菲利浦公司 | Two stage entrained gasification system and process |
| CN102816613A (en) * | 2012-07-25 | 2012-12-12 | 中国科学院广州能源研究所 | Homeothermal electrocatalysis assisted reforming purifying device for biomass fuel gas |
| CN103756735A (en) * | 2014-01-27 | 2014-04-30 | 淄博太沣环保工程有限公司 | Biomass gas catalytic reformer |
| CN105670710A (en) * | 2016-02-02 | 2016-06-15 | 河南农业大学 | Method for reforming biomass crude syngas by taking hydrogen peroxide as raw material |
| CN106701202A (en) * | 2017-01-05 | 2017-05-24 | 东华工程科技股份有限公司 | Apparatus and method used for mixing reaction of synthetic gas and coal and gas-solid-liquid grading separation of product |
| CN107557082A (en) * | 2017-10-24 | 2018-01-09 | 江门绿润环保科技有限公司 | A kind of synthesis gas reformer |
| CN110475844A (en) * | 2017-03-31 | 2019-11-19 | 日立造船株式会社 | Gas is modified furnace |
| CN110465281A (en) * | 2018-07-10 | 2019-11-19 | 吉林大学 | A kind of nickel magnesium sosoloid method for preparing catalyst |
| CN115786706A (en) * | 2022-11-28 | 2023-03-14 | 郴州金铖环保科技有限公司 | Method for reducing and smelting lead, bismuth and the like by using biomass gas |
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2007
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102124083A (en) * | 2008-08-15 | 2011-07-13 | 科诺科菲利浦公司 | Two stage entrained gasification system and process |
| CN102124083B (en) * | 2008-08-15 | 2014-02-26 | 拉默斯技术公司 | Two stage entrained gasification system and process |
| CN102816613A (en) * | 2012-07-25 | 2012-12-12 | 中国科学院广州能源研究所 | Homeothermal electrocatalysis assisted reforming purifying device for biomass fuel gas |
| CN102816613B (en) * | 2012-07-25 | 2014-03-05 | 中国科学院广州能源研究所 | Homeothermal electrocatalysis assisted reforming purifying device for biomass fuel gas |
| CN103756735A (en) * | 2014-01-27 | 2014-04-30 | 淄博太沣环保工程有限公司 | Biomass gas catalytic reformer |
| CN105670710A (en) * | 2016-02-02 | 2016-06-15 | 河南农业大学 | Method for reforming biomass crude syngas by taking hydrogen peroxide as raw material |
| CN105670710B (en) * | 2016-02-02 | 2018-05-08 | 河南省科学院能源研究所有限公司 | A kind of method using hydrogen peroxide as raw material reforming biomass crude synthesis gas |
| CN106701202A (en) * | 2017-01-05 | 2017-05-24 | 东华工程科技股份有限公司 | Apparatus and method used for mixing reaction of synthetic gas and coal and gas-solid-liquid grading separation of product |
| CN110475844A (en) * | 2017-03-31 | 2019-11-19 | 日立造船株式会社 | Gas is modified furnace |
| CN107557082A (en) * | 2017-10-24 | 2018-01-09 | 江门绿润环保科技有限公司 | A kind of synthesis gas reformer |
| CN110465281A (en) * | 2018-07-10 | 2019-11-19 | 吉林大学 | A kind of nickel magnesium sosoloid method for preparing catalyst |
| CN115786706A (en) * | 2022-11-28 | 2023-03-14 | 郴州金铖环保科技有限公司 | Method for reducing and smelting lead, bismuth and the like by using biomass gas |
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