CN1321187C - Efficient process of preparing hydrogen with botanical waste - Google Patents
Efficient process of preparing hydrogen with botanical waste Download PDFInfo
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- CN1321187C CN1321187C CNB2004100656835A CN200410065683A CN1321187C CN 1321187 C CN1321187 C CN 1321187C CN B2004100656835 A CNB2004100656835 A CN B2004100656835A CN 200410065683 A CN200410065683 A CN 200410065683A CN 1321187 C CN1321187 C CN 1321187C
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Abstract
The present invention relates to a biotechnology for the resource utilization of botanical waste materials, and also relates to a hydrogen preparing method. The botanical waste materials are degraded by rumen microbes, and liquid phase products are converted further. The degradation process comprises: (1), crushing or pulping the botanical waste materials into spare bed materials; (2), firstly inoculating the rumen microbes of ruminants to a fermenting tank for culture and acclimation, and then inoculating the cultured and acclimated rumen microbs of the ruminants into an anaerobic digestion reactor filled with the bed materials of the botanical waste materials and mineral buffer solutions; (3), starting and operating the anaerobic digestion reactor, and collecting generated gases with hydrogen, liquid phase products and solid phase products. When the conversion is further carried out, the liquid phase products are separated by a membrane. After the rumen microbs are removed, the liquid phase products are conveyed into a photosynthetic bacterium reactor, and degraded through photosynthetic bacteria, and the gases with hydrogen are collected again. The hydrogen is obtained after the purification is carried out. Most of the degraded products are finally converted into the hydrogen, and therefore, the hydrogen producing efficiency is improved. An experiment indicates that the hydrogen producing efficiency of each gram of degradation bed materials can reach 190 to 250 ml.
Description
Technical field:
The present invention relates to the biotechnology of botanical waste processing and recycling thereof, also relate to the preparation method of hydrogen.
Background technology:
A large amount of phyteral and the wastes thereof of the annual generation of China, wherein the agricultural crop straw annual production is amounted to 300,000,000 tons of standard coals approximately just more than 600,000,000 tons, and this is a huge energy reserves.Preciousness had both been wasted and limited resources at all a large amount of crop straw burnings of harvest season in annual rural area, again severe contamination environment.Strengthening waste resource and recycle and environment protection, help promoting the eubiosis, also is the needs of China's sustainable economic development.Therefore, the exploitation to the application technology as the second resource of botanical waste has crucial meaning.
Hydrogen all is widely used in many fields such as petrochemical complex, electronic industry and middle small power plants as a kind of important chemical material.Hydrogen also is a kind of important clean energy, is a kind of important fuel in aerospace industry.Hydrogen is the clean energy that can realize zero emission, therefore will have important purposes in electromobile, public transport and the hydrogen power generation in future.The fuel value height of hydrogen is 3 times of gasoline, 3.9 times of alcohol; Cleanliness without any pollution only produces water in the combustion processes, do not produce greenhouse gases carbonic acid gas and other harmful material.
In the prior art, the preparation of hydrogen comprises physico-chemical process and biotechnological means two big classes.Physico-chemical process prepares the hydrogen technology maturation, is existing main hydrogen preparation method, but its energy consumption height, the cost costliness.Compare with physico-chemical process, biological method produces that hydrogen has efficient, energy-conservation, economic dispatch plurality of advantages and the extremely great attention of countries in the world and numerous international organizations.Chinese patent CN 92114474.1 and U.S. Pat 6090266 have reported that all the application anaerobic activated sludge for producing the hydrogen microbial source, prepares the method for hydrogen by the anaerobic degradation of organic waste water.But the bed material that this class biological hydrogen production is adapted to is confined to contain the carbohydrate and the corresponding organic waste water thereof of sugar and starch class mostly.In the Chinese patent application 02148681.6 with agricultural crop straw through peracid pre-treatment, heating, then with alkali neutralization, use again compost through 100 ℃ of heat pre-treatment as microbial source fermentation produce hydrogen.Preprocessing process expense costliness in this method has limited its application aborning.In addition, 2003 the 48th the 4th phases of volume of Britain magazine " hydroscience and technology " (Water Science and Technology) had once been reported the method for utilizing rumen microorganism anaerobic degradation straw refuse.This method is earlier with crushed stalk, and intermittent then joining makes the botanical waste degraded in the anaerobic digestion reaction vessel of inoculating rumen microorganism, and its primary product is acetate, propionic acid, butyric acid and methane, does not wherein see the report that is useful on preparation hydrogen.
Summary of the invention:
The objective of the invention is to, provide a kind of and at first utilize rumen microorganism that botanical waste is degraded, its liquid product is further transformed, thereby can high-efficiency and low-cost ground prepare the method for hydrogen.
Technical scheme of the present invention realizes by the following method.
The method of efficiently utilizing botanical waste to prepare hydrogen of the present invention, comprise that the first step utilizes rumen microorganism that botanical waste is degraded and collect hydrogen gas, second step made its liquid product further transform, collect hydrogen gas and purification process obtains hydrogen; Have in the process that the first step is degraded: (1) is with the botanical waste fragmentation or pull an oar into standby bed material, (2) in ruminant tumor gastric, take out rumen microorganism, and be inoculated in the anaerobic digestion reaction vessel that fills botanical waste bed material and mineral substance damping fluid, (3) start the operation anaerobic digestion reaction vessel, make the phyteral acidication, (4) collect hydrogen gas, liquid product and the solid product that is produced respectively; It is characterized in that, described rumen microorganism of taking out in the ruminant tumor gastric, at first must be inoculated into and cultivate in the fermentor tank and tame, its inoculum size is the 5-30% of fermentor tank reaction volume, fill botanical waste bed material and mineral substance damping fluid in this fermentor tank, the concentration of phyteral bed material is 10-40g/L; The domestication condition is: the interpolation speed of botanical waste bed material is 20-40g/L/d, hydraulic detention time 12-24 hour, pH6.0-7.0, temperature is 30-43 ℃, stir speed (S.S.) 50-100 rev/min, the residence time 48-72 of botanical waste bed material in reactor hour, in institute's aerogenesis body composition, only detect hydrogen and carbonic acid gas continuous two weeks and when detecting, inoculate in the anaerobic digestion reaction vessel that fills botanical waste bed material and mineral substance damping fluid after promptly rumen microorganism is tamed fully less than methane; Make in the further process that transforms of its liquid product in second step, at first liquid product is separated with film, the filtering rumen microorganism, collect after making buffering salt in micromolecular short chain organic acid and alcohols and the solution see through film, being input to inoculation by existing method again has in the photosynthetic bacterium reactor of photosynthetic bacterium and collects hydrogen gas.Wherein said going on foot second makes in the further process that transforms of its liquid product, is 0.25-1.0 μ m in order to the membrane pore size of separating liquid product.
The method of efficiently utilizing botanical waste to prepare hydrogen of the present invention, the concrete operations step is:
1) broken phyteral: with phyteral such as agricultural crop straw, phyteral domestic refuse, waterplant pulverizing or making beating, final grain diameter is less than 8mm.
2) domestication rumen microorganism: the taking-up rumen microorganism is inoculated into the fermentor tank and tames in ruminant tumor gastric, and inoculum size is the 5-30% of fermentor tank reaction volume, fills botanical waste bed material and mineral substance damping fluid in this fermentor tank.The condition of rumen microorganism domestication is: it is 20-40g/L/d that bed materials such as stalk add speed, hydraulic detention time 12-24 hour, pH6.0-7.0, temperature is 30-43 ℃, stir speed (S.S.) 50-100 rev/min, 60 hours residence time in reactor of bed materials such as stalk.High density bed material and higher acidication speed have suppressed the growth and the breeding of methanobacteria, add breeding cycle generation that methanobacteria itself is long, and the methanobacteria in the reactor is cushioned the liquid wash-out gradually and comes out, methanobacteria completely dissolve in the final reactor.Therefore, the content of methane also reduces thereupon gradually in the gas-phase product, until last detection less than.When detecting less than the existing of methane when only detecting hydrogen and carbonic acid gas in continuous two all institutes aerogenesis body compositions, the rumen microorganism domestication is finished.Wherein said mineral substance damping fluid is that wear fragrant damping fluid or agate examined damping fluid etc., the fragrant damping fluid of wearing consist of NaHCO
35g/L, Na
2HPO
41.9g/L, KCl 0.5 g/L, NaCl 0.5g/L, MgCl
2.6H
2O 0.13g/L, CaCl
20.05g/L, urea 0.5g/L; Agate is examined the Na that consists of of damping fluid
2CO
33.1g/L, K
2CO
34.0g/L, Na
2H-PO
40.9g/L, K
2HPO
41.1g/L, MgCl
2.6H
2O 0.10g/L, CaCl
20.04g/L, urea 0.5g/L.
3) start anaerobic digestion reaction vessel: the rumen microorganism after will taming is inoculated into anaerobic digestion reaction vessel, feed 5-10 and doubly remove remaining oxygen to the rare gas element of reactor volume, keep reaction zone temperature 30-43 ℃, pH is 6.0-7.0, stir speed (S.S.) is 50-100 rev/min, and the concentration of bed materials such as stalk after the fragrant damping fluid dilution of wearing is 10-30g/L.Hydraulic detention time is 12-24 hour, and the bed material residence time is 48-72 hour, is 6.0-7.0 by the pH scope of adjusting concentration sodium hydroxide conditioned reaction district in the damping fluid, and keeps relative stablizing.When microorganism concn in the reaction zone reaches more than the 2.0g/L and keeps 2 weeks of steady running, then anaerobic digestion reaction vessel starts and finishes.
4) acidication of phyteral and collect hydrogen gas: the anaerobic digestion reaction vessel that reaches steady state, add the bed material concentration of the different corresponding adjustment damping fluid dilution of speed according to bed material, the interpolation speed mobility scale of bed material is 20-40g/L/d, hydraulic detention time is 12-24 hour, the bed material residence time is 48-72 hour, stir speed (S.S.) maintains 50-100 rev/min, and reaction zone pH scope is 6.0-7.0.Collect the hydrogen gas that produces, hydrogen content reaches 10-30% in this gas, handles obtaining pure hydrogen through simple purification.The reaction zone microorganism concn reaches 3-5g/L when reaching equilibrium state.Hydrogen produces efficient and reaches 50-100ml/g degraded bed material, produces sour efficient and reaches 0.2-0.4g organic acid/g bed material, and degradation efficiency reaches 55-75%.The residue of discharging is through precipitating and isolating liquid phase and solid product, and the liquid product that isolating liquid product and reactor upper end relief outlet are discharged merges.
5) liquid product is carried out membrane sepn: the filtering rumen microorganism, see through the short chain organic acid of film and the buffering salt in alcohols and the solution in the collection liquid product, the aperture of described film is 0.25-1.0 μ m.
6) operation of photosynthetic bacterium reactor and the second time collect gas: photosynthetic bacterium is inoculated in the photosynthetic bacterium reactor, and wherein the concentration of photosynthetic bacterium is 2g/L, and light intensity is the 2000-6000 lux.To be input to through the liquid product of membrane sepn in the photosynthetic bacterium reactor, and make it in photosynthetic reactor, further be converted into hydrogen and carbonic acid gas, and collect hydrogen and obtain pure hydrogen through after the purification process.Photosynthetic bacterium concentration is about 2-3g/L in the photosynthetic bacterium reactor, and hydraulic detention time is 2-3 days.To separate the back liquid product with 1-2ml/ minute speed and be pumped in the reactor, micromolecular short chain organic acid and alcohols are converted into hydrogen by photosynthetic bacterium.Generally, the organic acid hydrogen generation efficiency 100-160ml of generation after every gram bed material degraded, the pH value of solution value of producing the discharge of hydrogen reactor relief outlet rises to 8.5-9.5, can be used as damping fluid and reclaims the continuation use.
The present invention is a raw material with phyteral such as agricultural solid residue, waterplant, phyteral organic waste, utilize rumen microorganism efficient degradation in anaerobic digestion reaction vessel of domestication to produce organic acid, utilize the photosynthetic bacterium reactor that acidizing product is further transformed again and produce hydrogen.Because rumen microorganism is the very capable mixing microorganisms flora of occurring in nature decomposition of cellulose, and agricultural crop straw, pasture and water and domestic organic garbage are all had very strong capacity of decomposition.Therefore, handle with respect to the anaerobic activated sludge method, degradation efficiency of the present invention has improved 30-50%.Owing to methanobacteria in the pre-treatment is washed away, the hydrogen ion of release finally discharges with the form of hydrogen, has avoided the generation of methane in the anaerobic digestion process simultaneously, and the burning of methane and release will produce serious Greenhouse effect.The short chain organic acid that produces in the degradation process further is converted into hydrogen by photosynthetic bacterium, so the final major part of degraded product all is converted into hydrogen, has improved hydrogen generation efficiency greatly.Experiment shows that the hydrogen generation efficiency of every gram bed material can reach 190-250ml.In addition, be pumped into and recovered surge capability again after organic acid in the photosynthetic bacterium reactor liquid product is utilized, damping fluid as anaerobic digestion reaction vessel is reused, photosynthetic bacterium wherein can be used as the protein source of anaerobic digestion reaction vessel again, therefore accomplish the recycle of damping fluid, effectively save the energy, reduced cost.
Embodiment
Below by embodiment technical scheme of the present invention is further described.
Embodiment 1:
1, the stalk behind the collection reaping corn, airing was the particle of diameter less than 5mm with pulverizer with crushed stalk after 5 days.
2, get the 200ml rumen fluid from the fistula goat and transfer to rapidly in 5 liters of fermentor tanks, add corn stalk powder 80g and 3.8 liters of fragrant damping fluids of wearing, keeping the interior pH of reactor is 6.0-6.4, and 32 ℃ of temperature, stir speed (S.S.) are 60 rev/mins.The interpolation speed of straw powder remained 30g/L/d, and hydraulic detention time dropped to the 6th day 18 hours gradually and remains unchanged from 24 hours, and the residence time of straw powder in reactor is 60 hours.Detect the composition that produces composition in the gas every day, and when detecting less than methane when having only hydrogen and carbonic acid gas in continuous two all gaseous constituents, methanogen is removed fully, and the rumen microorganism domestication is finished.
3, the rumen microorganism after domestication is finished is inoculated in the anaerobic digestion reaction vessel, keeps 1.2L/ branch clock rate to charge into nitrogen 20 minutes, drives away residual oxygen in the reactor, guarantees the anaerobic state in the reactor.Overall reactor is amassed 4.9L, and wherein the reaction zone volume is 2.5 liters.The temperature of controlling reactor is 32 ℃, and pH is 6.0-6.4, and hydraulic detention time 16 hours stirred 30 seconds in per 2 minutes, and stir speed (S.S.) is 75 rev/mins.After 1 day, the maize straw of pulverizing is diluted to 10g/L (dry-matter meter) with the fragrant damping fluid of wearing, interpolation speed is increased to 25g/L/d after 7 days gradually from 10g/L/d.Residue after the degraded is discharged through outlet, is increased to 840mL/d (being equivalent to 72 hours bed material residence time) after 7 days gradually from the 250mL/d of beginning.When reaction zone pH is stabilized between the 6.0-6.4, it is above and keep 2 weeks of steady running that microorganism concn reaches 2.5g/L, and anaerobic digestion reaction vessel starts to be finished.
4, maize straw is 20g/L with the concentration of damping fluid dilution, and the speed that is pumped into reactor is 30g/L/d, hydraulic detention time 16 hours, and the speed that residue is discharged is 840ml/ days (being equivalent to 72 hours bed material residence time).According to the situation that reaction zone pH changes, in damping fluid, add sodium hydroxide, keep reaction zone pH between 6.0-6.4.When reaching balance, the reaction zone microorganism concn reaches 3.5-4.5g/L, and the degradation efficiency of maize straw reaches 72%, and the production efficiency of short chain organic acid reaches the 0.42g/g straw powder.Acetate 0.17g/g straw powder wherein, propionic acid 0.11g/g straw powder, butyric acid 0.10g/g straw powder, remaining is ethanol, isopropylformic acid, valeric acid and isovaleric acid.Hydrogen content reaches 32% in the gaseous constituent of collecting, and handles obtaining pure hydrogen through simple purification, and hydrogen output is the 70ml/g straw powder.
5, with solid phase in the residue and liquid product precipitate and separate, isolated liquid product and upper water-out mouth liquid product merge, and via hole diameter is 0.25 μ m membrane filtration, collect filtrate.
6, photosynthetic reactor is a cylindrical reactor, and diameter is 30mm, highly is 400mm, reaction zone volume 3.751; Continuously the filtrate of collecting is input in the photosynthetic reactor with fresh feed pump, the flow velocity of regulating fresh feed pump is that to make the residence time of solution in reactor be 2 days to 1.3ml/min; Inoculate photosynthetic hydrogen production bacterium-rhodopseudomonas acidophilus in advance in photosynthetic reactor, make its concentration reach 2g/l, continuing to provide intensity with incandescent lamp is 6000 lux luminous energy.The gas that produces is through air outlet and gas quantifier, and required hydrogen is isolated in collection.Processed waste liquid is discharged by water port.Through 2 months cultivation, the photosynthetic bacterium reactor reached equilibrium state, can stable continuous produce hydrogen and carbonic acid gas, handled promptly obtaining pure hydrogen through simple purification, and hydrogen gas production efficient is equivalent to 160ml hydrogen/g straw powder.The total hydrogen generation efficiency of former and later two reactors is 230ml hydrogen/g straw powder.The waste liquor PH value 8.5-9.2 that discharges reuses as damping fluid and protein source.
Embodiment 2:
1, collects family domestic garbage, reject the inorganics that wherein comprises, as stone, iron filings etc.It is less than the particle below the 6mm that cool solarization was pulverized after 5 days.
2, getting the 700ml rumen fluid from impotence pipe sheep transfers to rapidly in 5 liters of fermentor tanks, add comminuted plants matter organic waste 80g and 3.3 liters of fragrant damping fluids of wearing, keeping the interior pH of reactor is 6.3-6.7,37 ℃ of temperature, 60 hours bed material residence time, be easy to precipitation owing to containing the 10-30% inorganics of having an appointment in the phyteral organic waste, so stirring frequency changes 30 seconds/minute into, stir speed (S.S.) is 90 rev/mins.The interpolation speed of bed material remains 40g/L/d; Hydraulic detention time dropped to the 6th day 12 hours gradually and remains unchanged from 24 hours.Detect the composition that produces composition in the gas every day, and when detecting less than methane when having only hydrogen and carbonic acid gas in continuous two all gaseous constituents, methanogen is removed fully, and the rumen microorganism domestication is finished.
3, the rumen microorganism after domestication is finished goes in the anaerobic digestion reaction vessel with infusion, keeps 2.0L/ branch clock rate to charge into argon gas 15 minutes, drives away residual oxygen in the reactor, guarantees the anaerobic state in the reactor.Overall reactor is amassed 4.9L, and wherein the reaction zone volume is 2.5 liters.The temperature of controlling reactor is 35 ℃, and pH is 6.3-6.7, hydraulic detention time 12 hours, and stirring frequency is 30 seconds/minute, stir speed (S.S.) is 90 rev/mins.After 3 days, comminuted plants matter organic waste is diluted to 15g/L with the fragrant damping fluid of wearing, the phyteral organic waste adds speed and is increased to 30g/L/d after 7 days gradually from 10g/L/d.Residue after the degraded is discharged by pump 2 through outlet, is increased to 1000mL/d (being equivalent to 60 hours bed material residence time) after 7 days gradually from the 250mL/d of beginning.When reaction zone pH is stabilized between the 6.3-6.7, it is above and keep 2 weeks of steady running that microorganism concn reaches 2.0g/L, and anaerobic digestion reaction vessel starts to be finished.
4, the phyteral organic waste is with the concentration 20g/L of damping fluid dilution, and the speed that is pumped into reactor is 40g/L/d, and hydraulic detention time is 12 hours, and the speed that residue is discharged is 1000mL/d (being equivalent to the bed material residence time is 60 hours).According to the situation that reaction zone pH changes, in damping fluid, add sodium hydroxide, keep reaction zone pH between 6.4-6.7.When reaching balance, the reaction zone microorganism concn reaches 3-4g/L, the degradation efficiency of phyteral rubbish reaches 67%, the production efficiency of volatility short chain organic acid reaches 0.35g/g phyteral rubbish in the liquid product of discharging, acetate 0.18g/g phyteral rubbish wherein, propionic acid 0.08g/g phyteral rubbish, butyric acid 0.07g/g phyteral rubbish, remaining is isopropylformic acid, valeric acid, isovaleric acid and ethanol etc.Hydrogen content reaches 19% in the gaseous constituent of collecting, and handles promptly obtaining pure hydrogen through simple purification, and hydrogen yield is a 55ml/g phyteral rubbish
5, the separation of liquid product is as described in (5) among the embodiment 1, and using the aperture is 0.45 μ m membrane filtration, collects filtrate.
6, photosynthetic reactor is a cylindrical reactor, and diameter is 30mm, highly is 400mm, reaction zone volume 3.75L; Continuously the filtrate of collecting is input in the photosynthetic reactor with fresh feed pump, it is 1.5 days that the flow velocity 1.7ml/min of adjusting fresh feed pump makes the residence time of solution in reactor; Inoculate photosynthetic hydrogen production bacterium-rhodopseudomonas acidophilus in advance in photosynthetic reactor, making its concentration is 2g/L, and continuing to provide intensity with incandescent lamp is 6000 lux luminous energy.The gas that produces is isolated required hydrogen after collecting after through air outlet and gas dosage facility.The waste liquid of handling is discharged by water port.Through 2 months cultivation, the photosynthetic bacterium reactor reached equilibrium state, can stable continuous produce hydrogen and carbonic acid gas, obtained pure hydrogen through simple purification, and gas producing efficiency is 130ml hydrogen/gram phyteral rubbish.The total hydrogen generation efficiency of former and later two reactors is 185ml hydrogen/g phyteral rubbish.
Embodiment 3
1, the fresh stem or leaf of cattail of harvesting from the pond is broken into the soup compound of length less than 8mm with hollander.
2, getting the 1200ml rumen fluid from impotence pipe ox transfers to rapidly in 5 liters of fermentor tanks, stem or leaf of cattail 80g and 3.5 liters of fragrant damping fluids of wearing of adding pulpous state, keeping the interior pH of reactor is 6.3-6.8,41 ℃ of temperature, the residence time of the stem or leaf of cattail in reactor is 60 hours, stirring frequency is 30 seconds/2 minutes, and stir speed (S.S.) is 80 rev/mins.The interpolation speed of the stem or leaf of cattail remains 20g/L/d; Hydraulic detention time dropped to the 6th day 18 hours gradually and remains unchanged from 24 hours.Detect the composition that produces composition in the gas every day, and when detecting less than methane when having only hydrogen and carbonic acid gas in continuous two all gaseous constituents, methanogen is removed fully, and the rumen microorganism domestication is finished.
3, the rumen microorganism after domestication is finished is inoculated in the anaerobic digestion reaction vessel, keeps 2.0L/ branch clock rate to charge into argon gas 20 minutes, drives away residual oxygen in the reactor, guarantees the anaerobic state in the reactor.Overall reactor is amassed 4.9 L, and wherein the reaction zone volume is 2.5 liters.The temperature of controlling reactor is 41 ℃, and pH is 6.3-6.8, hydraulic detention time 18 hours, and stirring frequency is 30 seconds/2 minutes, stir speed (S.S.) is 80 rev/mins.After 3 days, the pulpous state stem or leaf of cattail is diluted to 10g/L (dry-matter meter) with the fragrant damping fluid of wearing, speed under load is increased to 25g/L/d after 7 days gradually from 10g/L/d.Residue after the degraded is discharged by pump 2 through outlet, is increased to 1250mL/d (being equivalent to 48 hours bed material residence time) after 7 days gradually from the 250mL/d of beginning.When reaction zone pH is stabilized between the 6.3-6.8, it is above and keep 2 weeks of steady running that microorganism concn reaches 2.0g/L, and anaerobic digestion reaction vessel starts to be finished.
4, the stem or leaf of cattail is with the concentration 20g/L of damping fluid dilution, and the speed that is pumped into reactor is 35g/L/d, and the speed that residue is discharged is 1250mL/ days (being equivalent to 48 hours bed material residence time).According to the situation that reaction zone pH changes, in damping fluid, add sodium hydroxide, keep reaction zone pH between 6.3-6.8.When reaching balance, the reaction zone microorganism concn reaches 3.5-4.0g/L, and the degradation efficiency of the stem or leaf of cattail reaches 57%, and the production efficiency of volatility short chain organic acid reaches the 0.37g/g stem or leaf of cattail.The acetate 0.18g/g stem or leaf of cattail wherein, the propionic acid 0.10g/g stem or leaf of cattail, the butyric acid 0.07g/g stem or leaf of cattail, remaining is ethanol, isopropylformic acid, valeric acid and isovaleric acid.Hydrogen content is 20% in the gas of collecting, and obtains pure hydrogen, the hydrogen yield 50ml/g stem or leaf of cattail through simple purification.
5, the separation of liquid product is as described in (5) among the embodiment 1, and using the aperture is 0.75 μ m membrane filtration.
6, photosynthetic reactor is a cylindrical reactor, and diameter is 30mm, highly is 400mm, reaction zone volume 3.75L; Continuously the filtrate of collecting is input in the photosynthetic reactor with fresh feed pump, it is 2 days that the flow velocity 1.3ml/min of adjusting fresh feed pump makes the residence time of solution in reactor; Inoculate photosynthetic hydrogen production bacterium-rhodopseudomonas acidophilus in advance in photosynthetic reactor, making its concentration is 2g/L, and continuing to provide intensity with incandescent light is 6000 lux luminous energy.The gas that produces is isolated required hydrogen after collecting after through air outlet and gas dosage facility.Processed waste water is discharged by water port.Through 2 months cultivation, the photosynthetic bacterium reactor reached equilibrium state, can stable continuous produce hydrogen and carbonic acid gas, handled promptly obtaining pure hydrogen through simple purification, and gas producing efficiency is 140ml hydrogen/g stem or leaf of cattail.The total hydrogen generation efficiency of former and later two reactors is 190ml hydrogen/g stem or leaf of cattail.
Claims (2)
1. method of utilizing botanical waste to prepare hydrogen comprises that the first step utilizes rumen microorganism that botanical waste is degraded, and second step made its liquid product further transform, produce hydrogen; Have in the process that the first step is degraded: (1) is with the botanical waste fragmentation or pull an oar into standby bed material, (2) in ruminant tumor gastric, take out rumen microorganism, and be inoculated in the anaerobic digestion reaction vessel that fills botanical waste bed material and mineral substance damping fluid, (3) start the operation anaerobic digestion reaction vessel, make the phyteral acidication, (4) collect hydrogen gas, liquid product and the solid product that is produced respectively; It is characterized in that, described rumen microorganism of taking out in the ruminant tumor gastric, at first must be inoculated into and cultivate in the fermentor tank and tame, its inoculum size is the 5-30% of fermentor tank reaction volume, fill botanical waste bed material and mineral substance damping fluid in this fermentor tank, wherein the concentration of phyteral bed material is 10-40g/L; The domestication condition is: the interpolation speed of botanical waste bed material is 20-40g/L/d, hydraulic detention time 12-24 hour, pH6.0-7.0, temperature is 30-43 ℃, stir speed (S.S.) 50-100 rev/min, the residence time 48-72 of botanical waste bed material in reactor hour, in institute's aerogenesis body composition, only detect hydrogen and carbonic acid gas continuous two weeks and when detecting, inoculate in the anaerobic digestion reaction vessel that fills botanical waste bed material and mineral substance damping fluid after promptly rumen microorganism is tamed fully less than methane; Make in the further process that transforms of its liquid product in second step, at first liquid product is separated with film, the filtering rumen microorganism, collect through the short chain organic acid of film and the buffering salt in alcohol and the solution, be input to inoculate in the photosynthetic bacterium reactor that photosynthetic bacterium is arranged by existing method again and carry out photosynthetic response and collect hydrogen gas.
2. the method for utilizing botanical waste to prepare hydrogen as claimed in claim 1 is characterized in that, described going on foot second makes in the further process that transforms of its liquid product, is 0.2-1.0 μ m in order to the membrane pore size of separating liquid product.
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| FR2961907B1 (en) * | 2010-06-29 | 2012-07-27 | Valorex Sa | METHOD FOR EVALUATING THE QUANTITY OF METHANE PRODUCED BY A RUMINANT SAID "A MEAT" |
| CN106978447A (en) * | 2017-04-01 | 2017-07-25 | 长兴微羽智能科技有限公司 | It is a kind of to comprehensively utilize the method that stalk and mud prepare hydrogen |
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