CN101270368A - Method for preparing hydrogen with biology and with utilization of organic waste water step - Google Patents
Method for preparing hydrogen with biology and with utilization of organic waste water step Download PDFInfo
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Abstract
The invention discloses a method of hydrogen production of biological cascade utilization on organic wastewater and relates to a method of producing hydrogen. The invention solves the existing problem of low conversion on biological hydrogen production with organic wastewater fermentation by using anaerobic activated sludge. The hydrogen production method of the invention is carried out as follows: firstly an anode chamber is in the anaerobic condition during startup procedure, anaerobic activated sludge is put into the anode chamber, the nutrient solution with pH value of 6.8 to 7.0 is introduced into the anode chamber, phosphate buffer is added into a cathode chamber, aeration is carried out in the cathode chamber in the previous 28 to 35 days of the startup procedure, startup is successful till the output voltage is continuously and steadily over 400 mV; secondly the organic wastewater is filled into the anode chamber from an inlet of the anode chamber and the organic wastewater is processed in the anode chamber, consequently hydrogen is obtained in the cathode chamber. The coulombic efficiency of the organic substrate conversion of the method reaches as high as over 80 percent, the electron transfer efficiency of transferring the cathode electron into hydrogen approaches to 100 percent, the purity of the hydrogen obtained in the cathode chamber in the entire process reaches 99.5 percent, the energy conversion efficiency of the entire process reaches over 80 percent, and the hydrogen yield calculated based on the input voltage is 288 percent.
Description
Technical field
The present invention relates to a kind of method of producing hydrogen.
Background technology
At present, the energy more than 80% and organic raw material come from fossil energy.Along with the exhausted of fossil energy and use the serious day by day of the environmental problem brought, the mankind will face serious energy dilemma and environmental pollution.Hydrogen is a kind of ideal new forms of energy, has aboundresources, combustion heat value height, cleanliness without any pollution, advantage of wide range of application.Thereby hydrogen extremely concern of countries in the world in future source of energy.Utilize biomass (organic waste water, stalk class agroforestry waste, organic waste etc.) to carry out microbial fermentation hydrogen manufacturing and possess multiple superiority such as pollution treatment, environmental protection and production capacity, DEVELOPMENT PROSPECT is wide.The microorganism hydrogen producing technology also is subjected to people's attention.At present, the research that utilizes anaerobism to carry out microorganism hydrogen manufacturing can be divided into three types substantially: the one, and adopt pure strain and technique for fixing to carry out microorganism hydrogen manufacturing, but strict because of its fermentation condition, also be in the laboratory study stage at present.The 2nd, utilize anaerobic activated sludge to carry out organic waste water fermentation method biological hydrogen production; The 3rd, the material decomposition of utilizing continuous on-fixed highly effective hydrogen yield bacterium to make to contain carbohydrate, protein etc. is produced hydrogen, and the hydrogen conversion of back two kinds of methods low (generally about 30%) has limited the practical application and the popularization of hydrogen.
Summary of the invention
The objective of the invention is to carry out the low problem of transformation efficiency of organic waste water fermentation method biological hydrogen production, and provide a kind of organic waste water step to utilize biological method of producing hydrogen in order to solve existing anaerobic activated sludge.
The biological hydrogen producing of organic waste water step utilization of the present invention is to carry out in having the double-chamber microbiological fuel cell of ion-exchange membrane, realize by following step: one, start reactor: the anolyte compartment is in anaerobic state in start-up course, anaerobic activated sludge is put into the anolyte compartment, the anaerobic activated sludge dosage accounts for anolyte compartment's volume 50%～60%, be that 6.8～7.0 nutritive medium feeds the anolyte compartment then with the pH value, the volume ratio of nutritive medium and anaerobic activated sludge is 1: 1, in cathode compartment, add the phosphate buffered saline buffer that accounts for cathode compartment volume 90% simultaneously, preceding 28～35 days air aerations in cathode compartment that start, aeration rate is 0.3～0.6m
3/ min when cell voltage is lower than 50mV, changes or additional nutrient solution fully, treats output voltage continually and steadily more than 400mV, and double-chamber microbiological fuel cell starts successfully; Two, the water-in of organic waste water by the anolyte compartment injected in the anolyte compartment, organism in the anode microbial film function yeast metabolism organic waste water in the anolyte compartment, hydrogen ion combines with electronics and obtains hydrogen in the cathode compartment, when cell voltage is lower than 50mV, change or be supplemented with organic waste water fully, the condition of hydrogen manufacturing operation: 25～30 ℃ of temperature of reaction, pH=6.8～7.1, boosting voltage is 250～800mV.
Anaerobic activated sludge in the step 1 is from the aeration tank of municipal sewage treatment or concentration basin obtains.
The nutritive medium of step 1 is formulated by 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 2g sodium acetate trihydrate, 1L deionized water and 2ml liquid microelement; Wherein every liter of liquid microelement is made up of the water of 600mg calcium chloride, 400mg magnesium chloride, 80mg iron protochloride, 400mg cobalt chloride, cupric chloride, 100mg Manganous chloride tetrahydrate, 10mg zinc chloride, 10mg sodium selenate, 15mg sodium wolframate, 20mg nickelous chloride, 100mg disodium ethylene diamine tetraacetate, 10mg ammonium molybdate and surplus.
The another kind of prescription of nutritive medium is as follows in the step 1: every liter of nutritive medium is made up of 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 1L deionized water, 10mL Wolfe mcg vitamin mixed solution, 10mL Wolfe trace quantity mineral substance element mixed solution and 10mmol sodium-acetate (electron donor); Wherein Wolfe mcg vitamin liquid mixed solution is by 2.0mg vitamin H, 2.0mg folic acid, 10.0mg vitamin B6,5.0mg VITMAIN B1,5.0mg riboflavin; 5.0mg niacin, 5.0mg calcium pantothenate, 0.1mg vitamin B12,5.0mg benzaminic acid, 5.0mg Thioctic Acid and 1.0L distilled water are formulated; Wolfe trace quantity mineral mixed solution is formulated by 1.5g nitrilotriacetic acid(NTA), 3.0g sal epsom, 0.5g manganous sulfate, 1.0g sodium-chlor, 0.1g ferrous sulfate, 0.1g cobalt chloride, 0.1g calcium chloride, 0.1g zinc sulfate, 0.01g copper sulfate, 0.01g aluminum potassium sulfate, 0.01g boric acid, 0.01g Sodium orthomolybdate and 1.0L distilled water.
Phosphate buffered saline buffer is made up of 5.618g SODIUM PHOSPHATE, MONOBASIC, 6.155g Sodium phosphate dibasic and 1000mL water in the step 1; The perhaps Tris-HCl buffered soln of pH=7.0.
The anode material of described double-chamber microbiological battery is carbon cloth or Graphite Electrodes; Its negative electrode is made by non-immersion carbon paper, and cathode surface is loaded with 0.35mg/cm
2Pt; Ion-exchange membrane is Nafion 117 films or anion-exchange membrane AMI-7001.
The principle of method: functional flora is electron donor with the organism in the start-up course, anode electrode is arrived in the electron transport that metabolism produces, arrive negative electrode via external circuit, combine consumption with oxygen and proton and form current circuit, functional flora shows in anode electrode with this understanding and forms function yeast microbial film (as shown in Figure 1) gradually, produce the organism in the functional microorganism metabolism organic waste water on the anode in the hydrogen process, hydrogen ion combines with electronics and obtains hydrogen in the cathode compartment.
The present invention transforms the coulombic efficiency of organic substrates (small molecules such as acetate) up to more than 80%, cathode electronics is converted into the electronics transformation efficiency of hydrogen near 100%, whole technology cathode compartment acquisition purity is 99.5% hydrogen, the integrated artistic energy transformation ratio is up to more than 80%, is 288% based on the hydrogen earning rate of input voltage.Processing product hydrogen experiment acquisition reactor unit volume hydrogen production potential result by different substrates is as follows: acetate is that substrate product hydrogen top speed is 1.5m
3d
-1m
-3It is 0.11m that cellulosic substrate is produced the hydrogen top speed
3d
-1m
-3It is 1.23m that glucose sugar substrate produces the hydrogen top speed
3d
-1m
-3It is 1.04m that the lactic acid substrate produces the hydrogen top speed
3d
-1m
-3It is 0.14m that the valeric acid substrate produces the hydrogen top speed
3d
-1m
-3
The present invention all obtains considerable progress in macromolecular substance such as small organic molecule utilization and glucose, Mierocrystalline cellulose are handled.The present invention is combined with the present microorganism ferment for hydrogen production, utilize the organic waste water of the discharge of ferment for hydrogen production technology, it is carried out zymophyte collect in the double-chamber microbiological battery that separates after re-adjustment pH value back feeds startup, realize the utilization of organic waste water organic waste water step; Can effectively solve the problem that fermentation end products composition can't recovered energy, further obtain hydrogen in the auxiliary lower step utilization of electrochemistry, thereby provide new way for breaking through the hydrogen transformation efficiency that improves unit matrix.This method makes full use of the end products of many biological fermentations or complete processing more, can handle organic waste water completely and reclaim biomass energy with the form of hydrogen.Combining with fermentation process for making hydrogen of the present invention with unit matrix hydrogen transformation efficiency from 3molH
2/ mol glucose is brought up to 7～11molH
2/ mol glucose.
Description of drawings
Fig. 1 is the schematic diagram that the present invention produces hydrogen, 1 expression anode among Fig. 1, and 2 expression external circuit, 3 expression negative electrodes, 4 expression cathode compartments, 5 expression ion-exchange membranees, 6 expression anolyte compartments, 7 express water pipe, 8 expression water inlet pipes.Fig. 2 is microbiological fuel cell start-up course voltage and a potential ph diagram ph in the embodiment 12, among Fig. 2 ●-expression anolyte compartment redox potential, zero expression cathode compartment redox potential ,-▲-expression load voltage curve (being that the electrogenesis domestication produces voltage, load 1000 Ω).Fig. 3 is the auxiliary hydrogen production by biological technology running current periodogram (boosting voltage 0.6V) of bioelectrochemistry in the embodiment 12, among Fig. 3-▲-the indication circuit current curve ,-◇-expression boosting voltage curve.Fig. 4 is the auxiliary microorganism electrode potential ph diagram ph of bioelectrochemistry in the embodiment 12, among Fig. 4-●-expression anodic oxidation reduction potential curve ,-zero-expression cathode oxidation reduction potential curve.Fig. 5 is the auxiliary hydrogen production by biological figure (boosting voltage 0.6V) of bioelectrochemistry in the embodiment 12 ,-zero-expression gas volume among Fig. 5 ,-▲-metabolism of expression acetate.Fig. 6 is the scanning electron mirror figure of anode microbial film function yeast of the present invention.
Embodiment
Embodiment one: the biological hydrogen producing of organic waste water step utilization is to carry out in having the double-chamber microbiological battery of ion-exchange membrane, realize by following step: one, start reactor: the anolyte compartment is in anaerobic state in start-up course, anaerobic activated sludge is put into the anolyte compartment, the anaerobic activated sludge dosage accounts for anolyte compartment's volume 50%～60%, be that 6.8～7.0 nutrient solution feeds the anolyte compartment then with the pH value, the volume ratio of nutrient solution and anaerobic activated sludge is 1: 1, in cathode compartment, add the phosphate buffered saline buffer that accounts for cathode compartment volume 90% simultaneously, preceding 28～35 days air aerations in cathode compartment that start, aeration rate is 0.3～0.6m
3/ min when cell voltage is lower than 50mV, changes or additional nutrient solution fully, treats output voltage continually and steadily more than 400mV, and double-chamber microbiological fuel cell starts successfully (forming more stable functional biological film on anode, startup needs 1～2 month); Two, the water-in of organic waste water by the anolyte compartment injected in the anolyte compartment, organism in the anode microbial film function yeast metabolism organic waste water in the anolyte compartment, hydrogen ion combines with electronics and obtains hydrogen in the cathode compartment, when cell voltage is lower than 50mV, change or be supplemented with organic waste water fully, the condition of technological operation: 25～30 ℃ of temperature of reaction, pH=6.8～7.1, boosting voltage is 250～800mV.
The effect of phosphate buffered saline buffer is to make its pH to remaining on 7.0 in order to keep the cathode compartment environment in the step 1, keeps the proton concentration in the solution simultaneously, and the anaerobic activated sludge in the step 1 is from the aeration tank of municipal sewage treatment or concentration basin obtains.What present embodiment organic waste water adopted is city domestic sewage, especially is rich in the processing waste water of organic molecule composition, and water outlet waste water etc. for example ferments.Be main dominant microflora (see figure 6) with Shiva Bordetella (Shewanella sp.) and Rhodopseudomonas (Pseudomonas sp.) in the anode microbial film function yeast that forms of anode surface after testing.
Present embodiment transforms the coulombic efficiency of organic substrates up to more than 80%, cathode electronics is converted into the electronics transformation efficiency of hydrogen near 100%, whole technology cathode compartment acquisition purity is 99.5% hydrogen, the integrated artistic energy transformation ratio is up to more than 80%, is 288% based on the hydrogen earning rate of input voltage.Processing product hydrogen experiment acquisition reactor unit volume hydrogen production potential result by different substrates is as follows: acetate is that substrate product hydrogen top speed is 1.5m
3d
-1m
-3It is 0.11m that cellulosic substrate is produced the hydrogen top speed
3d
-1m
-3It is 1.23m that glucose sugar substrate produces the hydrogen top speed
3d
-1m
-3It is 1.04m that the lactic acid substrate produces the hydrogen top speed
3d
-1m
-3It is 0.14m that the valeric acid substrate produces the hydrogen top speed
3d
-1m
-3
Embodiment two: what present embodiment and embodiment one were different is: the nutritive medium of step 1 is formulated by 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 2g sodium acetate trihydrate, 1L deionized water and 2ml liquid microelement.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment two were different is: every liter of liquid microelement is made up of the water of 600mg calcium chloride, 400mg magnesium chloride, 80mg iron protochloride, 400mg cobalt chloride, cupric chloride, 100mg Manganous chloride tetrahydrate, 10mg zinc chloride, 10mg sodium selenate, 15mg sodium wolframate, 20mg nickelous chloride, 100mg disodium ethylene diamine tetraacetate (EDTA disodium), 10mg ammonium molybdate and surplus.Other is identical with embodiment two.
Embodiment four: what present embodiment and embodiment one were different is: every liter of nutritive medium is made up of 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 1L deionized water, 10mL Wolfe mcg vitamin mixed solution, 10mLWolfe trace quantity mineral substance element mixed solution and 10mmol sodium-acetate in the step 1.Other is identical with embodiment one.
The Wolfe mcg vitamin liquid mixed solution and the Wolfe trace quantity mineral mixed solution of present embodiment need keep in Dark Place.
Wolfe mcg vitamin liquid mixed solution is by 2.0mg vitamin H, 2.0mg folic acid, 10.0mg vitamin B6,5.0mg VITMAIN B1,5.0mg riboflavin; 5.0mg niacin, 5.0mg calcium pantothenate, 0.1mg vitamins B 12,5.0mg benzaminic acid, 5.0mg Thioctic Acid and 1.0L distilled water are formulated.
Wolfe trace quantity mineral mixed solution is formulated by 1.5g nitrilotriacetic acid(NTA), 3.0g sal epsom, 0.5g manganous sulfate, 1.0g sodium-chlor, 0.1g ferrous sulfate, 0.1g cobalt chloride, 0.1g calcium chloride, 0.1g zinc sulfate, 0.01g copper sulfate, 0.01g aluminum potassium sulfate, 0.01g boric acid, 0.01g Sodium orthomolybdate and 1.0L distilled water; Wolfe trace quantity mineral mixed solution compound method is as follows: earlier nitrilotriacetic acid(NTA) is added in the 500ml distilled water, regulate pH to 7.5 with dissolving with NaOH then, then water is added to 1L, again other composition is added mixing successively and get final product.
Embodiment five: what present embodiment and embodiment one were different is: phosphate buffered saline buffer is made up of 5.618g SODIUM PHOSPHATE, MONOBASIC, 6.155g Sodium phosphate dibasic and 1000mL water in the step 1.Other is identical with embodiment one.
Embodiment six: what this enforcement and embodiment one were different is that phosphate buffered saline buffer is the Tris-HCl buffered soln of pH=7.0.Other is identical with embodiment one.
Embodiment seven: what present embodiment and embodiment one were different is: the anode material of double-chamber microbiological battery is carbon cloth or Graphite Electrodes.Other is identical with embodiment one.
Embodiment eight: what present embodiment and embodiment one were different is: the negative electrode of double-chamber microbiological battery is made by non-immersion carbon paper, and cathode surface is loaded with 0.35mg/cm
2Pt.Other is identical with embodiment one.
Embodiment nine: what present embodiment and embodiment one were different is: ion-exchange membrane is Nafion 117 films or anion-exchange membrane AMI-7001.Other is identical with embodiment one.
Present embodiment intermediate ion exchange membrane is the commercial goods.
Embodiment ten: what present embodiment and embodiment one were different is: aeration rate is 0.35～0.5m in the step 1
3/ min.
Embodiment 11: what present embodiment and embodiment one were different is: aeration rate is 0.4m in the step 1
3/ min.
Embodiment 12: present embodiment combines embodiment one with present microorganism ferment for hydrogen production technology, the discharge of ferment for hydrogen production technology organic useless carried out zymophyte collects in the double-chamber microbiological battery after re-adjustment pH value back feeds startup, boosting voltage 0.6V in the step 3 wherein, function yeast is to be obligate anaerobic flora of representative etc. with bacterial strain B49 (Ethanologenbacterium hit B49).B
49Be middle temperature neutrophilia fermenting bacteria, its fermented type is an ethanol-type, can be at 28～43 ℃, grow under pH3.3～8.5 conditions; Optimum growth temperature is 37 ℃, and optimum growh pH value is about 4.8; Dai Shiwei 7.2h.B
49Q
H2Be 25.0mmolH
2/ gdrycellh, Y
H2Be 1813.8ml/L-culture, hydrogen production potential occupy the world level prostatitis.Its fermentation end products composition such as subordinate list 1.
Present embodiment is to serve as inoculation bacterium source with Harbin urban sewage disposal plant aeration tank and concentration basin active sludge.
Table 1
Can find after deliberation: terminal small molecules organic composition acetate of ethanol-type fermentation and proportion of ethanol are up to (seeing Table 1) more than 90%.But these materials still can't utilize and handle as waste water, have not only wasted the energy but also have not met the aim of current cleaner production.Therefore, the auxiliary biological thorough utilization that the coupling of hydrogen novel method then can realize small organic molecules such as acetate, ethanol of producing of electrochemistry further obtains hydrogen simultaneously.Ethanol-type fermentation two other fermented types of one of carbon tip product constituent ratio have more advantage and potentiality.The combining with fermentation process for making hydrogen with unit matrix hydrogen transformation efficiency from 3molH
2/ mol glucose is brought up to 7～11molH
2/ mol glucose (as Fig. 4, shown in Figure 5).
Present embodiment in double-chamber microbiological start battery process, in the anolyte compartment redox potential basicly stable-500mV near; The redox potential of environment under the air aeration state in the cathode compartment can reach 200mV.Along with the advantage enrichment of function yeast, the voltage that can obtain progressively to raise at 1000 Ω load two ends output tames that output voltage can reach 450mV after one month, and output rating is 32mW/m
2When the acetate in the waste water is depleted to a certain degree, output voltage can quickly fall near the 50mV, mean this moment in the waste water organism base conditioning finish, replenish more than the new horizontal 400mV that is rich in before outward current can go back up to rapidly behind the organic waste water.(referring to Fig. 2)
Along with the metabolism of acetate in the water inlet, circuital current demonstrates periodic variation as seen from Figure 3, and bigger electronics circulation is promptly arranged in the circuit when the microbial metabolism organic substrates, and the generation of hydrogen can continue to take place; The electronics that function yeast produces after nutriment is depleted to certain level reduces rapidly, and circuital current decreases, and hydrogen produces speed to be reduced, and output descends; After replenishing new nutriment, microbial metabolism recovers rapidly, and the electron transport amount increases, and circuital current returns to higher level.
Present method will further be expanded fermentative hydrogen production technology, not only thoroughly handle organic waste water, also improve the conversion capability of hydrogen simultaneously, reduce the cost of fermentation method bio-hydrogen production technology, further improve the bio-hydrogen production technology industrialization technical support is provided.As can see from Figure 2, the electropotential of anode room environmental is progressively stable in start-up course, and the anolyte compartment is stable at-500mV, is stable at 200mV under the cathode compartment aeration condition, output voltage progressively improve and the peak value 300mV that tends towards stability near.Because nutriment consumption demonstrates the reduction of output voltage, add or change after the acetate nutritive medium output voltage returning to peak level rapidly and be increased near the 500mV in the time of the 28th day.This expression system starts successfully, as long as the sufficient technology of nutriment can continuous service.Fig. 3 has added the product hydroformylation stage behind the boosting voltage.Can see first day and add the stable impressed voltage of 0.58V at the electrode two ends, system current peak occurred about 3 days, along with the consumption system of nutriment presents periodic running status, and reflect that from levels of current the state of system is stable gradually, produce the hydrogen system structure and finish, can collect hydrogen at negative electrode.Fig. 4 is Fig. 3 electropotential monitoring curve of the same period.Can see that the electropotential behind the product stabilized hydrogen is very steady, cathode compartment is-600mV that the anolyte compartment is-450mV.Product hydrogen effect after system is stable as shown in Figure 5.Can see that acetate consumed in the cycle of 220mg, cathode compartment is collected 40ml gas, and by the gas chromatographic analysis gas purity, the hydrogen yield that can calculate this preliminary operation acquisition is 0.5mol hydrogen/mol acetate.When system is stablized by the functional microorganism that adheres on the sem observation anode carbon cloth electrode as shown in Figure 6.
Claims (10)
1, organic waste water step utilizes biological method of producing hydrogen, it is characterized in that the biological hydrogen producing of organic waste water step utilization is to carry out in having the double-chamber microbiological fuel cell of ion-exchange membrane, realize by following step: one, start reactor: the anolyte compartment is in anaerobic state in start-up course, anaerobic activated sludge is put into the anolyte compartment, the anaerobic activated sludge dosage accounts for anolyte compartment's volume 50%～60%, be that 6.8～7.0 nutritive medium feeds the anolyte compartment then with the pH value, the volume ratio of nutritive medium and anaerobic activated sludge is 1: 1, in cathode compartment, add the phosphate buffered saline buffer that accounts for cathode compartment volume 90% simultaneously, preceding 28～35 days air aerations in cathode compartment that start, aeration rate is 0.3～0.6m
3/ min when cell voltage is lower than 50mV, changes or additional nutrient solution fully, treats output voltage continually and steadily more than 400mV, and double-chamber microbiological fuel cell starts successfully; Two, the water-in of organic waste water by the anolyte compartment injected in the anolyte compartment, organism in the anode microbial film function yeast metabolism organic waste water in the anolyte compartment, hydrogen ion combines with electronics and obtains hydrogen in the cathode compartment, when cell voltage is lower than 50mV, change or be supplemented with organic waste water fully, the condition of hydrogen manufacturing operation: 25～30 ℃ of temperature of reaction, pH=6.8～7.1, boosting voltage is 250～800mV.
2, utilize biological method of producing hydrogen according to the described organic waste water step of claim 1, it is characterized in that anaerobic activated sludge in the step 1 is that aeration tank or concentration basin from municipal sewage treatment obtains.
3, utilize biological method of producing hydrogen according to the described organic waste water step of claim 1, the nutritive medium that it is characterized in that step 1 is formulated by 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 2g sodium acetate trihydrate, 1L deionized water and 2ml liquid microelement; Wherein every liter of liquid microelement is made up of the water of 600mg calcium chloride, 400mg magnesium chloride, 80mg iron protochloride, 400mg cobalt chloride, cupric chloride, 100mg Manganous chloride tetrahydrate, 10mg zinc chloride, 10mg sodium selenate, 15mg sodium wolframate, 20mg nickelous chloride, 100mg disodium ethylene diamine tetraacetate, 10mg ammonium molybdate and surplus.
4, utilize biological method of producing hydrogen according to the described organic waste water step of claim 1, it is characterized in that every liter of nutritive medium is made up of 0.31g ammonium chloride, 0.13mg Repone K, 5.618g two hypophosphite monohydrate sodium dihydrogens, 6.155g two hypophosphite monohydrate disodium hydrogens, 1L deionized water, 10mL Wolfe mcg vitamin mixed solution, 10mL Wolfe trace quantity mineral substance element mixed solution and 10mmol sodium-acetate in the step 1; Wherein Wolfe mcg vitamin liquid mixed solution is by 2.0mg vitamin H, 2.0mg folic acid, 10.0mg vitamin B6,5.0mg VITMAIN B1,5.0mg riboflavin; 5.0mg niacin, 5.0mg calcium pantothenate, 0.1mg vitamin B12,5.0mg benzaminic acid, 5.0mg Thioctic Acid and 1.0L distilled water are formulated; Wolfe trace quantity mineral mixed solution is formulated by 1.5g nitrilotriacetic acid(NTA), 3.0g sal epsom, 0.5g manganous sulfate, 1.0g sodium-chlor, 0.1g ferrous sulfate, 0.1g cobalt chloride, 0.1g calcium chloride, 0.1g zinc sulfate, 0.01g copper sulfate, 0.01g aluminum potassium sulfate, 0.01g boric acid, 0.01g Sodium orthomolybdate and 1.0L distilled water.
5, state organic waste water step according to claim 1 and utilize biological method of producing hydrogen, it is characterized in that phosphate buffered saline buffer is made up of 5.618g SODIUM PHOSPHATE, MONOBASIC, 6.155g Sodium phosphate dibasic and 1000mL water in proportion in the step 1.
6, utilize biological method of producing hydrogen according to the described organic waste water step of claim 1, it is characterized in that phosphate buffered saline buffer is the Tris-HCl buffered soln of pH=7.0 in the step 1.
7, utilize biological method of producing hydrogen according to the described organic waste water step of claim 1, the anode material that it is characterized in that the double-chamber microbiological battery is carbon cloth or Graphite Electrodes.
8, utilize biological method of producing hydrogen according to the described organic waste water step of claim 1, it is characterized in that the negative electrode of double-chamber microbiological battery is made by non-immersion carbon paper, cathode surface is loaded with 0.35mg/cm
2Pt.
9, utilize biological method of producing hydrogen according to the described organic waste water step of claim 1, it is characterized in that ion-exchange membrane is Nafion 117 films or anion-exchange membrane AMI-7001.
10, utilize biological method of producing hydrogen according to the described organic waste water step of claim 1, it is characterized in that aeration rate is 0.35～0.5m in the step 1
3/ min.
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