CN103242922A - Method for preparing fuel gas by burning biomass - Google Patents
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- CN103242922A CN103242922A CN2013102096540A CN201310209654A CN103242922A CN 103242922 A CN103242922 A CN 103242922A CN 2013102096540 A CN2013102096540 A CN 2013102096540A CN 201310209654 A CN201310209654 A CN 201310209654A CN 103242922 A CN103242922 A CN 103242922A
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Abstract
The invention provides a method for preparing fuel gas by burning biomass. The method comprises the following steps of: firstly, smashing, namely smashing a biomass reaction material; secondly, gasifying, namely gasifying the smashed biomass reaction material to generate synthesis gas; thirdly, primarily purifying, namely removing particulate matter, acidic gas and tar in the synthesis gas obtained by the step two; fourthly, deeply purifying, namely removing sulphide in the synthesis gas obtained by primary purification; fifthly, carrying out methanation, namely carrying out methanation on the synthesis gas purified by the step four to obtain fuel gas; and sixthly, improving quality of gas, namely removing saturated steam, CO2 and unreacted H2 and N2 in the fuel gas subjected to methanation. By adopting the method, two different catalysts are used, so that content of tar produced by burning the biomass is reduced, and gas production rate is increased.
Description
Technical field
The present invention relates to the combustion gas preparing technical field, relate in particular to the method that a kind of biomass combustion prepares combustion gas.
Background technology
The energy is the basic substance of human survival and development.It is the important leverage of national economy and social development.Along with development of human society, energy-output ratio constantly increases.At present, world energy consumption is mainly based on non-renewable fossil energies such as coal, oil and natural gas.According to the world energy sources microstructure Prediction, the whole world will increase by 55% to the primary energy source demand between the year two thousand thirty in 2005, and average growth rate per annum is 1.8%.Energy demand will reach 25,300,000,000 t standard coals.Fossil oil will be the main source of primary energy source, increases in the total amount the energy demand to the year two thousand thirty in 2005 to account for 84%.Because economic sustained and rapid development, the energy demand of China will continue to increase, according to prediction, the primary energy source demand of China will be doubled many, and 2005 is 2,500,000,000 t standard coals, and the year two thousand thirty is 5,500,000,000 t standard coals, and average growth rate per annum is 3.2%.
Because a large amount of exploitations and the consumption of fossil oil have discharged a large amount of excess energies and carbon element, have destroyed natural energy and carbon balance, ecological and environment serious pollution and destruction have been caused.The burning utilization of fossil energy causes that the concentration of carbonic acid gas and other greenhouse gases constantly increases in the atmosphere, is to cause global temperatures to rise and one of reason of climate change; The sustainable growth of fossil oil consumption will continue to increase whole world dust, oxynitride, carbon monoxide, carbonic acid gas and the sulphur dioxide emission relevant with the energy.According to estimates, the CO2 emissions of China will be increased to 11,400,000,000 t of the year two thousand thirty from 5,100,000,000 t in 2005, and sulphur dioxide emission will be increased to 3,000 ten thousand of the year two thousand thirty from 2,600 ten thousand t in 2005.Therefore seeking and developing renewable substitute energy becomes the inevitable requirement that promotes social sustainable development.
Renewable energy source is recycled Energy resources, mainly contains water energy, wind energy, underground heat, sun power, sea energy and biomass energy etc., does not have the resource exhaustion problem.In these new forms of energy, because large-scale water power has potential Ecological Environment Risk, and wind energy, underground heat, sun power and sea energy etc. have regional resource restriction, greatly develop and be restricted and query.In these renewable energy sources, biomass energy occupies critical role with its exclusive characteristics at energy field.Greatly develop biomass energy to alleviating China's energy scarcity situation, utilize the problem of environmental pollution that causes in the process to have vital role to solving fossil oil.
Biomass energy has become the focus that the investigator pays close attention to as a kind of renewable, free of contamination clean energy.Gasifying biomass is a kind of biomass thermal chemical conversion process, significant progress has been arranged in recent years, particularly in fields such as power generation and heat supplies.The main component of biomass rough gas is H
2, CO, CO
2, CH
4, tar and other light hydrocarbon etc., biomass rough gas is converted into low H
2The synthetic gas of/CO mol ratio (≈ 1) is the perfect gas of synthetic liquid fuel.
Utilize biological fuel gas to prepare synthetic gas as unstripped gas and come into one's own gradually in recent years, but in the thick combustion gas because CH
4At high temperature disproportionation reaction carbon deposit and tar condensation cracking carbon deposit take place in cracking carbon deposit, CO at low temperatures, the covering catalyst active sites, even block reaction tubes.Another key issue of using is that the GAS QUALITY of biomass rough gas is lower, and the content of tar is higher, therefore, the present invention is by using biomass to prepare in the process of combustion gas, two kinds of catalyzer are provided, thereby reduce the tar content that biomass combustion produces, improve factor of created gase.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of biomass combustion prepares combustion gas, by using two kinds of different catalyzer, thereby reduces the tar content that biomass combustion produces, and improves factor of created gase.
For solving the problems of the technologies described above, the invention provides the method that a kind of biomass combustion prepares combustion gas, it comprises:
The first step is pulverized, and the biomass reaction material is pulverized;
Second step, gasification, the biomass reaction material gasification with after pulverizing generates synthetic gas;
In the 3rd step, particulate matter, sour gas and tar in the synthetic gas of second step acquisition are removed in rough purification;
The 4th step, deep purifying, the sulfide in the synthetic gas that the removal rough purification obtains;
The 5th step, methanation, the synthetic gas methanation with after the purification of the 4th step obtains combustion gas;
The 6th step, gas upgrading, saturated steam, CO in the combustion gas after the removal methanation
2And unreacted H
2And N
2
Wherein, described second step is specially puts into the biomass gasification reaction device with building sand and calcined dolomite catalyzer as fluidizing medium, with the Fe-NiO/TiO of carbon nanotube (CNT) grafting
2Catalyzer is put into fixed bed catalytic reactor, open the electrical heater that is positioned at biomass gasification reaction device outside the biomass gasification reaction device is carried out preheating, when temperature of reactor reaches preset temperature and keeps when constant, the beginning bubbling air passes through 20min again, the reaction material feeding biomass gasification reaction device with water vapor and after pulverizing, carry out gasification reaction, reaction times is 25min～35min, and the mass ratio of water vapor and reaction material is 0.3:1～0.5:1, obtains synthetic gas.
Wherein, described the 3rd step is specially through cyclonic separator removes particulate matter, removes tar and water by icy salt solution condenser and cotton linters filter.
Wherein, described the 4th step is specially adopts ZnO or CuO bed to remove remaining sulfide, is reduced to 0.1mg/m by the sulfide in the gas behind ZnO bed or the CuO bed
3Below.
Wherein, described the 5th step is specially Ni/SiO
2-CaO-Fe
2O
3Catalyzer is put into methanator, and the synthetic gas after purifying is fed in the methanator, reaches Ni/SiO under the temperature more than 300 ℃
2-CaO-Fe
2O
3Change into methane under the effect of catalyzer.
Wherein, described the 6th water vapour that is specially in the combustion gas of step is removed CO by flash distillation, condensation, absorption or membrane sepn mode
2Remove H by pressure swing adsorption decarbonization method (PSA), physisorphtion, gas film partition method (UOP)
2, N
2Can remove by membrane separation technique.
The present invention also provides a kind of biomass combustion to prepare the method for combustion gas, and it comprises:
The first step is pulverized, and the biomass reaction material is pulverized, and the size after reaction material is pulverized is in 300 μ m～1mm scope;
In second step, gasification will be put into the biomass gasification reaction device as building sand and the calcined dolomite catalyzer of fluidizing medium, with the Fe-NiO/TiO of carbon nanotube (CNT) grafting
2Catalyzer is put into fixed bed catalytic reactor, open the electrical heater that is positioned at biomass gasification reaction device outside the biomass gasification reaction device is carried out preheating, when temperature of reactor reaches preset temperature and keeps when constant, the beginning bubbling air passes through 20min again, the reaction material feeding biomass gasification reaction device with water vapor and after pulverizing, carry out gasification reaction, reaction times is 25min～35min, and the mass ratio of water vapor and reaction material is 0.3:1～0.5:1, obtains synthetic gas;
In the 3rd step, rough purification is removed particulate matter with synthetic gas through cyclonic separator, removes tar and water by icy salt solution condenser and cotton linters filter;
In the 4th step, deep purifying adopts ZnO or CuO bed to remove remaining sulfide, is reduced to 0.1mg/m by the sulfide in the gas behind ZnO bed or the CuO bed
3Below;
In the 5th step, methanation is with Ni/SiO
2-CaO-Fe
2O
3Catalyzer is put into methanator, and the synthetic gas after purifying is fed in the methanator, reaches Ni/SiO under the temperature more than 300 ℃
2-CaO-Fe
2O
3Change into methane under the effect of catalyzer, obtain combustion gas;
The 6th step, the gas upgrading, the water vapour in the combustion gas is removed CO by flash distillation, condensation, absorption or membrane sepn mode
2Remove H by pressure swing adsorption decarbonization method (PSA), physisorphtion, gas film partition method (UOP)
2, N
2Can remove by membrane separation technique, obtain needed combustion gas.
Wherein, described calcined dolomite Preparation of catalysts is as follows: rhombspar is pulverized, filtered out the particle that particle diameter is 0.3～0.45mm, at 900 ℃ temperature lower calcination 4h.
Wherein, the Fe-NiO/TiO of described carbon nanotube (CNT) grafting
2The concrete preparation method of catalyzer is as follows:
The first step, Fe-NiO/TiO
2Preparation of catalysts takes by weighing 68g tetrabutyl titanate solution, adds 377mL dehydrated alcohol and 26.75g nitric acid, and stirring obtains solution A; With 0.404gFe (NO
3)
39H
2O, 2.619g Ni (NO
3) 26H
2O is dissolved in the 215mL deionized water, obtains solution B. and solution B is added drop-wise in the solution A, stirs 2h, leave standstill 20h, 120 ℃ of oven dry. the speed with 3 ℃/min is warming up to 500 ℃, the Fe-NiO/TiO of roasting 3h. preparation
2
In second step, get the Fe-NiO/TiO for preparing
210g places fluidized-bed reactor, regulates nitrogen flow 5L/min, makes catalyst fluidization. and be warming up to 500 ℃, behind the temperature-stable, the flow of acetylene gas with 25L/h be passed in the reactor in the question response device, behind the reaction 10min, close acetylene gas, keep N
2Flow is constant, is down to room temperature, the catalyzer CNT/Fe-Ni/TiO of preparation
2
Wherein, described Ni/SiO
2-CaO-Fe
2O
3The Preparation of catalysts method is specially:
With mine tailing sand dry 12h under 120 ℃, 15min mills after the drying, choose the particle that particle diameter is not more than 70 μ m, place High Temperature Furnaces Heating Apparatus afterwards, handle 4h at 850 ℃ roasting temperatures, take out the back secondary 5min that mills, by stoichiometry incipient impregnation nickelous nitrate (AR) aqueous solution, 600 ℃ of roasting 4h make nickeliferous 10% Ni/SiO
2-CaO-Fe
2O
3Catalyzer.
Beneficial effect of the present invention:
Biomass combustion provided by the invention prepares the method for combustion gas, by using two kinds of different catalyzer, thereby reduces the tar content that biomass combustion produces, and improves factor of created gase.
Description of drawings
Fig. 1 biomass gasification device structure iron;
The Fe-NiO/TiO of Fig. 2 carbon nanotube (CNT) grafting
2The Raman spectrum of catalyzer;
The Fe-NiO/TiO of Fig. 3 carbon nanotube (CNT) grafting
2The XRD spectra of catalyzer;
The XRD spectra of Fig. 4 mine tailing sand;
Gained Ni/SiO after Fig. 5 roasting
2-CaO-Fe
2O
3The XRD spectra of catalyzer;
Fig. 6 the present invention adopts biomass to prepare the schema of combustion gas.
Embodiment
The invention provides the method that a kind of biomass combustion prepares combustion gas, it comprises:
The first step is pulverized, and reaction material is pulverized;
In second step, gasification will be put into the biomass gasification reaction device as building sand and the calcined dolomite catalyzer of fluidizing medium, with the Fe-NiO/TiO of carbon nanotube (CNT) grafting
2Catalyzer is put into fixed bed catalytic reactor, open the electrical heater that is positioned at biomass gasification reaction device outside the biomass gasification reaction device is carried out preheating, when temperature of reactor reaches preset temperature and keeps when constant, the beginning bubbling air, pass through 20min again, reaction material feeding biomass gasification reaction device with water vapor and after pulverizing, carry out gasification reaction, reaction times is 25min～35min, the mass ratio of water vapor and reaction material is 0.3:1～0.5:1, obtains synthetic gas, and it is the gasification heat supply that the advantage in this step is directly to adopt air, gasification temperature is lower, contains a certain amount of CH in the crude synthesis gas
4, reduced follow-up methanation reaction heat release to the pressure of reactor and catalyzer, whole combined coefficient height;
The 3rd step, rough purification, particulate matter is removed by modes such as centrifugal, filtrations in the synthetic gas that produces, tar is removed by pyrolysis method, catalystic pyrolysis or wet washing, sour gas can pass through tertiary alcohol absorption process, these methods all are affiliated field methods commonly used, preferably remove particulate matter through cyclonic separator, remove tar and water by icy salt solution condenser and cotton linters filter;
The 4th step, deep purifying, because of methanation catalyst in the subsequent technique to pollutent in the gas, especially sulfide is extremely sensitive, need carry out deep purifying enter methanator after the gas adjustment before.General ZnO or the CuO bed of adopting removed remaining sulfide, can be reduced to 0.1mg/m by the sulfide in the gas behind ZnO bed or the CuO bed
3Below;
In the 5th step, methanation is with Ni/SiO
2-CaO-Fe
2O
3Catalyzer is put into methanator, and the synthetic gas after purifying is fed in the methanator, reaches Ni/SiO at a certain temperature
2-CaO-Fe
2O
3Change into methane under the effect of catalyzer, the methanation reaction temperature is generally all more than 300 ℃, add water the work-ing life that steam can prolong catalyzer in methanator, the water vapour add-on is under pressure, temperature effect, and temperature is more low, the more high institute of pressure water requirement is more many.
In the 6th step, the gas upgrading contains saturated steam, CO in the gas behind the methanation reaction
2And unreacted H
2And small amount of N
2, water vapour can be removed CO by modes such as flash distillation, condensation, absorption or membrane sepn
2The removal technology has pressure swing adsorption decarbonization method (PSA), physisorphtion, gas film partition method (UOP), H
2, N
2Can remove by membrane separation technique.
In the described the first step, size after reaction material is pulverized is in 300 μ m～1mm scope, not obvious than the performance of the gasification difference between the small particle size under the high temperature, but to the particle of particle diameter greater than lmm, rising along with temperature of reaction, gas yield increases gradually, but generally less than the factor of created gase of small particle size.This behavior shows the increase along with particle diameter, and particle surface is restricted gradually with inner heat passage deleterious.
Preheating temperature in described second step is 60 ℃～65 ℃.
The temperature of the steam that feeds in described second step is 150 ℃～155 ℃, and pressure is 0.4Mpa～0.6Mpa.
Described calcined dolomite Preparation of catalysts is as follows: rhombspar is pulverized, filtered out the particle that particle diameter is 0.3～0.45mm, at 900 ℃ temperature lower calcination 4h.
The Fe-NiO/TiO of described carbon nanotube (CNT) grafting
2The concrete preparation method of catalyzer is as follows:
The first step, Fe-NiO/TiO
2Preparation of catalysts takes by weighing 68g tetrabutyl titanate solution, adds 377mL dehydrated alcohol and 26.75g nitric acid, and stirring obtains solution A; With 0.404gFe (NO
3)
39H
2O, 2.619g Ni (NO
3) 26H
2O is dissolved in the 215mL deionized water, obtains solution B. and solution B is added drop-wise in the solution A, stirs 2h, leave standstill 20h, 120 ℃ of oven dry. the speed with 3 ℃/min is warming up to 500 ℃, the Fe-NiO/TiO of roasting 3h. preparation
2
In second step, get the Fe-NiO/TiO for preparing
210g places fluidized-bed reactor, regulates nitrogen flow 5L/min, makes catalyst fluidization. and be warming up to 500 ℃, behind the temperature-stable, the flow of acetylene gas with 25L/h be passed in the reactor in the question response device, behind the reaction 10min, close acetylene gas, keep N
2Flow is constant, is down to room temperature, the catalyzer CNT/Fe-Ni/TiO of preparation
2
Wherein, prepared catalyzer CNT/Fe-Ni/TiO
2Reference area be 89.6m
2/ g.
Described Ni/SiO
2-CaO-Fe
2O
3The Preparation of catalysts method is specially:
With mine tailing sand dry 12h under 120 ℃, 15min mills after the drying, choose the particle that particle diameter is not more than 70 μ m, place High Temperature Furnaces Heating Apparatus afterwards, handle 4h at 850 ℃ roasting temperatures, take out the back secondary 5min that mills, by stoichiometry incipient impregnation nickelous nitrate (AR) aqueous solution, 600 ℃ of roasting 4h make nickeliferous 10% Ni/SiO
2-CaO-Fe
2O
3Catalyzer.
Gasification installation of the present invention comprises biomass gasification reaction device, feeding device, vapour generator, air compressor, cyclonic separator and fixed bed catalytic reactor.
Described biomass gasification reaction device is a normal pressure bubbling fluidized bed, the bottom internal diameter is 40mm, the top internal diameter is 60mm, the fluidized-bed total height is 1400mm, in the upper and lower of fluidized-bed a cylindrical electric furnace is arranged respectively, electric furnace carries out temperature control by temperature controller, in the fluidized-bed bottom one dispersion plate is installed, grid distributor thickness is 3mm, the aperture that to be evenly distributed with 25 diameters above be 1mm.
Described vapour generator is connected with the biomass gasification reaction device by pipeline, under meter is installed on the pipeline, feeding device is connected with the biomass gasification reaction device by pipeline, air compressor is connected by the bottom of pipeline with the biomass gasification reaction device, the top of biomass gasification reaction device is connected with cyclonic separator, cyclonic separator is connected with fixed bed catalytic reactor, in inlet end and the outlet side of fixed bed catalytic reactor gas sampling assembly is installed all.
Below adopt embodiment to describe embodiments of the present invention by reference to the accompanying drawings in detail, how the utilisation technology means solve technical problem to the present invention whereby, and the implementation procedure of reaching technique effect can fully understand and implements according to this.
As shown in Figure 1, gasification installation provided by the invention comprises normal pressure bubbling fluidized bed 1, feeding device 2, vapour generator 3, air compressor 4, cyclonic separator 5 and fixed bed catalytic reactor 6, described vapour generator 3 is connected with normal pressure bubbling fluidized bed 1 by pipeline, under meter 7 is installed on the pipeline, feeding device 2 is connected with normal pressure bubbling fluidized bed 1 by pipeline, air compressor 4 is connected by the bottom of pipeline with normal pressure bubbling fluidized bed 1, the top of normal pressure bubbling fluidized bed 1 is connected with cyclonic separator 5, cyclonic separator 5 is connected with fixed bed catalytic reactor 6, inlet end and outlet side at fixed bed catalytic reactor 6 all are equipped with gas sampling assembly 7, this normal pressure bubbling fluidized bed, the bottom internal diameter is 40mm, the top internal diameter is 60mm, the fluidized-bed total height is 1400mm, a cylindrical electric furnace 8 is respectively arranged in the upper and lower of fluidized-bed, electric furnace 8 carries out temperature control by temperature controller, in normal pressure bubbling fluidized bed 1 bottom one dispersion plate 9 is installed, grid distributor thickness is 3mm, the aperture that to be evenly distributed with 25 diameters above be 1mm.
The preparation of embodiment 1 calcined dolomite
Rhombspar is pulverized, filtered out the particle that particle diameter is 0.3～0.45mm, at 900 ℃ temperature lower calcination 4h, namely.
The Fe-NiO/TiO of embodiment 2 carbon nanotubes (CNT) grafting
2Preparation of catalysts
The catalyst surface feature adopts ASAP2010 specific surface and aperture analyser (Micrometrics company) to analyze.
Take by weighing 68g tetrabutyl titanate solution, add 377mL dehydrated alcohol and 26.75g nitric acid, stirring obtains solution A; With 0.404gFe (NO
3)
39H
2O, 2.619g Ni (NO
3)
26H
2O is dissolved in the 215mL deionized water, obtains solution B. and solution B is added drop-wise in the solution A, stirs 2h, leave standstill 20h, 120 ℃ of oven dry. the speed with 3 ℃/min is warming up to 500 ℃, the Fe-NiO/TiO of roasting 3h. preparation
2, prepared Fe-Ni/TiO
2Reference area be 63.0m
2/ g gets the Fe-NiO/TiO for preparing
2Catalyzer 10g places fluidized-bed reactor, regulates nitrogen flow 5L/min, makes catalyst fluidization. be warming up to 500 ℃, behind the temperature-stable, the flow of acetylene gas with 25L/h is passed in the reactor in the question response device, behind the reaction 10min, close acetylene gas, keep N
2Flow is constant, is down to room temperature, the catalyzer CNT/Fe-Ni/TiO of preparation
2, prepared catalyzer CNT/Fe-Ni/TiO
2Reference area be 89.6m
2/ g.
The Raman spectrometry
That shown in Figure 2 is sample CNT/Fe-Ni/TiO behind the growth CNT
2Raman spectrum. from spectrogram as can be seen, what apparent in view peak .TiO2 crystal occurred at 146,197,393,518,639cm-1 place anatase structuredly has six Raman vibration modes A1g+2B1g+3Eg, and corresponding raman spectra is respectively 515 (A
1g+ B
1g, ν
1+ ν
2), 398 (B
1g, ν
3), 640 (E
g, ν
4), 198 (E
g, ν
5) and 147 (E
g, ν
6) cm
-1. hence one can see that the TiO of growth behind the CNT
2Mainly still exist with anatase crystal, 1350 and 1580cm
-12 bigger peaks occurred, this two places raman spectra all belongs to the characteristic peak of multi-walled carbon nano-tubes, corresponds respectively to unordered Raman modes D mould and the Graphene E of inducing
2gOptical mode.Concerning carbon nanotube, can adopt D ratio (Id/Ig) interval and the interval intensity of G to characterize the integrity of carbon pipe carbonization structure.In general, I
d/ I
gValue more low, illustrate that the greying crystalline condition of carbon pipe is more good.According to spectrogram, calculate I
d/ I
g=0.78, illustrate that the CNT degree of graphitization of growth is than higher.
XRD spectra
As shown in Figure 3, for the catalyst sample FNT of the CNT that do not grow, diffraction peak is the characteristic peak of anatase titanium dioxide, the diffraction peak of other materials do not occur. after grafting growth CNT, and a small amount of TiO
2Change rutile structure into. simultaneously, Ni (111) characteristic peak ° has appearred in 2 θ=44.51, show in the process of growth CNT, NiO among the FNT is reduced into the feeding quantity that metal Ni. prepares per sample, can calculate in the FNT sample molar content of Fe and Ni be respectively 0.5% and 4.5%. because Fe content is lower, can not effectively be detected by XRD, and after NiO is reduced generation metal Ni, because metal Ni at high temperature sintering grows up, so can be detected by XRD.The transition metal that reduction generates such as Ni become the catalytic active center of CNT growth.The characteristic peak of CNT (2 θ=26.0 °) and TiO
2(101) diffraction peak overlapping, make TiO
2° diffraction peak intensity of locating strengthens in 2 θ=25.3.
Embodiment 3Ni/SiO
2-CaO-Fe
2O
3Preparation of catalysts
With mine tailing sand dry 12h under 120 ℃, 15min mills after the drying, choose the particle that particle diameter is not more than 70 μ m, place High Temperature Furnaces Heating Apparatus afterwards, handle 4h at 850 ℃ roasting temperatures, take out the back secondary 5min that mills, by stoichiometry incipient impregnation nickelous nitrate (AR) aqueous solution, 600 ℃ of roasting 4h make nickeliferous 10% Ni/SiO
2-CaO-Fe
2O
3Catalyzer.
Specific surface area is carried out at employing ASAP2010 specific surface and aperture analyser (Micrometrics company), with support powder dry 20min under 120 ℃ of temperature, after cooling, with Al
2O
3Be reference, H
2Do carrier gas, under liquid nitrogen temperature, adsorb N
2, use the BET formula calculated specific surface area, after testing, Ni/SiO
2-CaO-Fe
2O
3The specific surface area of catalyzer is 8.7m
2/ g.
Fig. 4 is the XRD spectra of mine tailing sand, in 2 θ=20.8 °, SiO appearred in 26.6 °, 36.5 °, 39.4 °, 50.1 °, 59.9 °, 68.1 ° and 68.3 ° of positions
2Characteristic diffraction peak; In 2 θ=23.1 °, CaCO appearred in 29.4 °, 36.0 °, 43.2 °, 47.1 °, 47.5 °, 48.5 ° and 57.4 ° of positions
3Characteristic diffraction peak; In 2 θ=28.5 °, FeS appearred in 33.0 °, 37.0 °, 40.7 °, 47.4 °, 56.3 °, 59.0 ° and 64.3 ° of positions
2Characteristic diffraction peak; In 2 θ=28.5 °, Zn appearred in 33.0 °, 47.4 °, 56.3 °, 59.0 °, 69.3 °, 76.6 ° and 78.9 ° of positions
xFe
1-xThe S characteristic diffraction peak; In 2 θ=20.8 °, calcium zeopan characteristic diffraction peak appearred in 26.6 °, 29.5 °, 39.3 °, 42.4 °, 45.5 °, 50.0 °, 60.0 ° and 67.8 ° of positions.The XRD characterization result shows that the husky main thing phase composite of mine tailing is SiO
2, CaCO
3, FeS
2, Zn
xFe
1-xS, calcium zeopan.
Fig. 5 is the XRD spectra of the gained complex carrier after the roasting, compares with Fig. 4, and noticeable change has appearred in the crystal phase structure of product.Original CaCO in the mine tailing
3, FeS
2, Zn
xFe
1-xComposition characteristics diffraction peaks such as S disappear, in 2 θ=24.1 °, 33.1 °, 35.6 °, 40.8 °, 49.4 °, 54.0 °, 62.4 ° and 64.0 ° of positions have showed Fe
2O
3Characteristic diffraction peak, in 2 θ=25.4 °, CaSO appearred in 31.3 °, 38.6 °, 40.8 °, 49.1 ° positions
4Characteristic diffraction peak shows that chemical reaction, FeS have taken place support material in high-temperature calcination process
2Be oxidized to Fe
2O
3, and gas-phase product SO
xAgain with CaCO
3Degradation production CaO partial reaction generates CaSO
4Simultaneously, component Zn
xFe
1-xS is oxidized to ZnO and Fe2O
3, the ZnO high dispersing is not seen its characteristic diffraction peak. and when maturing temperature was 900 ℃, the characteristic diffraction peak intensity of calcium zeopan had enhancing, and calcium zeopan existence form is changed to ceramic phase or sosoloid by the clay based composite oxide.
As shown in Figure 6, consider the corn stalk of 1kg to be worth doing be ground into about 500 μ m particle, to put into normal pressure bubbling fluidized bed 1 as the calcined dolomite catalyzer 50g of the building sand of fluidizing medium and embodiment 1 preparation, with the Fe-NiO/TiO of carbon nanotube (CNT) grafting of 65g embodiment 2 preparations
2Catalyzer is put into fixed bed catalytic reactor, open the 8 pairs of normal pressure bubbling fluidized beds of electrical heater 1 that are positioned at normal pressure bubbling fluidized bed 1 outside and carry out preheating, when normal pressure bubbling fluidized bed 1 temperature reaches 65 ℃ of preset temperatures and keeps when constant, the beginning bubbling air, pass through 20min again, reaction material feeding normal pressure bubbling fluidized bed 1 with water vapor and after pulverizing, the temperature of steam is 155 ℃, pressure is 0.6Mp, carry out gasification reaction, reaction times is 35min, and the corn stalk bits after pulverizing are sent into the speed of 0.8kg/h, and water vapour is sent into the speed of 0.4kg/h, obtain synthetic gas, the synthetic gas that produces is removed particulate matter through cyclonic separator, removes tar and water by icy salt solution condenser and cotton linters filter, can be reduced to 0.1mg/m by the sulfide in the ZnO bed gas
3Below, with the Ni/SiO of 40g embodiment 3 preparations
2-CaO-Fe
2O
3Catalyzer is put into methanator, the synthetic gas after purifying is fed in the methanator, at 400 temperature ℃ following and Ni/SiO
2-CaO-Fe
2O
3Change into methane under the effect of catalyzer, methanation reaction obtains the water vapour of combustion gas and removes CO by condensing mode
2Remove H by the absorption carbon rejection processes
2, N
2Can remove by membrane separation technique, obtain combustion gas.
Comparative example
Adopt the method identical with embodiment 4 to prepare combustion gas, distinguish the Fe-NiO/TiO that is not adopt carbon nanotube (CNT) grafting
2Catalyzer and Ni/SiO
2-CaO-Fe
2O
3Catalyzer.
After the reaction aerogenesis was stablized 5min, every interval 3min with the gas collector sampling once took a sample 3 times altogether, and test result is got 3 times mean value.After finishing experiment, when the automatic cool to room temperature of temperature, collect gasification lime-ash and tar.
Catalytic gasification generates gas content and detects with portable gas chromatograph (Agilent3000A micro-GC).
The results are shown in Table 1.
Table 1 liang group measurement result relatively
| Group | Tar yield/% | Lime-ash productive rate/% | Factor of created gase/ |
| Embodiment | |||
| 4 | 0 | 2.01 | 3.96 |
| Comparative example | 0.73 | 8.93 | 0.63 |
This intellecture property of primary enforcement that all are above-mentioned is not set restriction this product innovation of other forms of enforcement and/or novel method.Those skilled in the art will utilize this important information, and foregoing is revised, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on product innovation of the present invention.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (10)
1. a biomass combustion prepares the method for combustion gas, it is characterized in that, comprising:
The first step is pulverized, and the biomass reaction material is pulverized;
Second step, gasification, the biomass reaction material gasification with after pulverizing generates synthetic gas;
In the 3rd step, particulate matter, sour gas and tar in the synthetic gas of second step acquisition are removed in rough purification;
The 4th step, deep purifying, the sulfide in the synthetic gas that the removal rough purification obtains;
The 5th step, methanation, the synthetic gas methanation with after the purification of the 4th step obtains combustion gas;
The 6th step, gas upgrading, saturated steam, CO in the combustion gas after the removal methanation
2And unreacted H
2And N
2
2. biomass combustion as claimed in claim 1 prepares the method for combustion gas, it is characterized in that: described second step is specially puts into the biomass gasification reaction device with building sand and calcined dolomite catalyzer as fluidizing medium, with the Fe-NiO/TiO of carbon nanotube (CNT) grafting
2Catalyzer is put into fixed bed catalytic reactor, open the electrical heater that is positioned at biomass gasification reaction device outside the biomass gasification reaction device is carried out preheating, when temperature of reactor reaches preset temperature and keeps when constant, the beginning bubbling air passes through 20min again, the reaction material feeding biomass gasification reaction device with water vapor and after pulverizing, carry out gasification reaction, reaction times is 25min～35min, and the mass ratio of water vapor and reaction material is 0.3:1～0.5:1, obtains synthetic gas.
3. biomass combustion as claimed in claim 1 or 2 prepares the method for combustion gas, it is characterized in that: described the 3rd step is specially through cyclonic separator removes particulate matter, removes tar and water by icy salt solution condenser and cotton linters filter.
4. prepare the method for combustion gas as the described biomass combustion of claim 1 to 3, it is characterized in that: described the 4th step is specially adopts ZnO or CuO bed to remove remaining sulfide, is reduced to 0.1mg/m by the sulfide in the gas behind ZnO bed or the CuO bed
3Below.
5. prepare the method for combustion gas as the described biomass combustion of claim 1 to 4, it is characterized in that: described the 5th step is specially Ni/SiO
2-CaO-Fe
2O
3Catalyzer is put into methanator, and the synthetic gas after purifying is fed in the methanator, reaches Ni/SiO under the temperature more than 300 ℃
2-CaO-Fe
2O
3Change into methane under the effect of catalyzer.
6. prepare the method for combustion gas as the described biomass combustion of claim 1 to 5, it is characterized in that: the water vapour that described the 6th step is specially in the combustion gas is removed CO by flash distillation, condensation, absorption or membrane sepn mode
2Remove H by pressure swing adsorption decarbonization method (PSA), physisorphtion, gas film partition method (UOP)
2, N
2Can remove by membrane separation technique.
7. a biomass combustion prepares the method for combustion gas, it is characterized in that, comprising:
The first step is pulverized, and the biomass reaction material is pulverized, and the size after reaction material is pulverized is in 300 μ m～1mm scope;
In second step, gasification will be put into the biomass gasification reaction device as building sand and the calcined dolomite catalyzer of fluidizing medium, with the Fe-NiO/TiO of carbon nanotube (CNT) grafting
2Catalyzer is put into fixed bed catalytic reactor, open the electrical heater that is positioned at biomass gasification reaction device outside the biomass gasification reaction device is carried out preheating, when temperature of reactor reaches preset temperature and keeps when constant, the beginning bubbling air passes through 20min again, the reaction material feeding biomass gasification reaction device with water vapor and after pulverizing, carry out gasification reaction, reaction times is 25min～35min, and the mass ratio of water vapor and reaction material is 0.3:1～0.5:1, obtains synthetic gas;
In the 3rd step, rough purification is removed particulate matter with synthetic gas through cyclonic separator, removes tar and water by icy salt solution condenser and cotton linters filter;
In the 4th step, deep purifying adopts ZnO or CuO bed to remove remaining sulfide, is reduced to 0.1mg/m by the sulfide in the gas behind ZnO bed or the CuO bed
3Below;
In the 5th step, methanation is with Ni/SiO
2-CaO-Fe
2O
3Catalyzer is put into methanator, and the synthetic gas after purifying is fed in the methanator, reaches Ni/SiO under the temperature more than 300 ℃
2-CaO-Fe
2O
3Change into methane under the effect of catalyzer, obtain combustion gas;
The 6th step, the gas upgrading, the water vapour in the combustion gas is removed CO by flash distillation, condensation, absorption or membrane sepn mode
2Remove H by pressure swing adsorption decarbonization method (PSA), physisorphtion, gas film partition method (UOP)
2, N
2Can remove by membrane separation technique, obtain needed combustion gas.
8. prepare the method for combustion gas as the described biomass combustion of claim 1 to 7, it is characterized in that: described calcined dolomite Preparation of catalysts is as follows: rhombspar is pulverized, filtered out the particle that particle diameter is 0.3～0.45mm, at 900 ℃ temperature lower calcination 4h.
9. prepare the method for combustion gas as the described biomass combustion of claim 1 to 8, it is characterized in that: the Fe-NiO/TiO of described carbon nanotube (CNT) grafting
2The concrete preparation method of catalyzer is as follows:
The first step, Fe-NiO/TiO
2Preparation of catalysts takes by weighing 68g tetrabutyl titanate solution, adds 377mL dehydrated alcohol and 26.75g nitric acid, and stirring obtains solution A; With 0.404gFe (NO
3)
39H
2O, 2.619g Ni (NO
3) 26H
2O is dissolved in the 215mL deionized water, obtains solution B. and solution B is added drop-wise in the solution A, stirs 2h, leave standstill 20h, 120 ℃ of oven dry. the speed with 3 ℃/min is warming up to 500 ℃, the Fe-NiO/TiO of roasting 3h. preparation
2
In second step, get the Fe-NiO/TiO for preparing
210g places fluidized-bed reactor, regulates nitrogen flow 5L/min, makes catalyst fluidization. and be warming up to 500 ℃, behind the temperature-stable, the flow of acetylene gas with 25L/h be passed in the reactor in the question response device, behind the reaction 10min, close acetylene gas, keep N
2Flow is constant, is down to room temperature, the catalyzer CNT/Fe-Ni/TiO of preparation
2
10. prepare the method for combustion gas as the described biomass combustion of claim 1 to 9, it is characterized in that: described Ni/SiO
2-CaO-Fe
2O
3The Preparation of catalysts method is specially,
With mine tailing sand dry 12h under 120 ℃, 15min mills after the drying, choose the particle that particle diameter is not more than 70 μ m, place High Temperature Furnaces Heating Apparatus afterwards, handle 4h at 850 ℃ roasting temperatures, take out the back secondary 5min that mills, by stoichiometry incipient impregnation nickelous nitrate (AR) aqueous solution, 600 ℃ of roasting 4h make nickeliferous 10% Ni/SiO
2-CaO-Fe
2O
3Catalyzer.
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| CN105582932A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Biomass synthetic gas catalyst, preparation method and application thereof |
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