CN100348711C - Series-parallel multi-stage compounding apparatus and method for producing hydrogen by biomass continceous fermentation - Google Patents
Series-parallel multi-stage compounding apparatus and method for producing hydrogen by biomass continceous fermentation Download PDFInfo
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- CN100348711C CN100348711C CNB2005100486519A CN200510048651A CN100348711C CN 100348711 C CN100348711 C CN 100348711C CN B2005100486519 A CNB2005100486519 A CN B2005100486519A CN 200510048651 A CN200510048651 A CN 200510048651A CN 100348711 C CN100348711 C CN 100348711C
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- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
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- C12M23/00—Constructional details, e.g. recesses, hinges
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- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/12—Means for regulation, monitoring, measurement or control, e.g. flow regulation of temperature
- C12M41/18—Heat exchange systems, e.g. heat jackets or outer envelopes
- C12M41/24—Heat exchange systems, e.g. heat jackets or outer envelopes inside the vessel
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Abstract
The present invention discloses a series-parallel multi-stage composite device and a method for the continuous fermentation hydrogen production of biomass, and relates to a device and a method for the fermentative hydrogen production of biomass by using immobilized microorganisms. A first stage is a fermentative tank for provenance source cultivation and fermentation, a second stage is an assistant fermentative tank for assisting provenance source cultivation and fermentation, a third stage is a main fermentative tank, and the last stage is fermentative tanks in n-series connection (n>3), wherein 1% to 10% W/ V of mixed immobilized bacteria is respectively put into the first stage and the second stage; other stages have no immobilized blocks. The method comprises the following technical processes: the materials are mainly fed in the first stage and the third stage; the raw materials are prepared in the first stage, and prepared in a rough way in the third stage; roughing-out raw materials are in the third stage. Liquid in each stage flows towards the next stage in a natural traveling way without power supplying. Gas in each stage is respectively collected or treated in concentration by a tee. The series-parallel multi-stage composite device and the multi-stage succession of composite technology can compensate for and balance dehydrogenase existing in a single fermentative tank and a rule that produced hydrogen presents alternately. The series-parallel multi-stage composite device solves a non-uniformity problem, and thus, the utilization rate of the raw materials for hydrogen production is sufficiently enhanced; the high efficiency and the continuous stability of hydrogen production are realized.
Description
Affiliated technical field
The invention belongs to method and the device of immobilized microorganism biomass fermentation and hydrogen production.
Technical background
The biomass hydrogen preparation raw material sources are extensive, when obtaining Hydrogen Energy, can handle organic pollutant, are the hot fields of modern biochemistry research.
In recent years, more to associated biomolecule reactor, technical process and the immobilized microorganism of fermentation and hydrogen production both at home and abroad at the biomass fermentation and hydrogen production technology to the research of the anaerobic digestion techniques method of biomass fermentation and hydrogen production, bigger progress is also arranged.Calendar year 2001 Narendra Kumar, people such as Debabrata Das utilize the packed bed bio-reactor, with the Exocarpium cocois (Cocos nucifera L) is fixedly bacterial classification Enterobacter cloacae IIT-BT08 glucose fermentation product hydrogen of material, and the maximum hydrogen production that obtains is 2.1 times that ferment in batches under the equal conditions.G.Chittibabu in 2005, Kaushik Nath, people such as Debabrata Das utilize anaerobism coherent film expanded bed (AAFEB), with the bacterial strain Escherichia coli BL21 after the reorganization is that inoculum carries out glucose fermentation product hydrogen, energy transformation efficiency by calculating gas (wherein glucose calculates by sucrose) is 26.68%, and the productive rate of hydrogen is 3.12mol H
2/ (molglucose).2003, Feng-Yung Chang, Chiu-Yue Lin etc. have confirmed that up-flow anaerobic sludge blanket can be used as the bio-reactor of biomass fermentation and hydrogen production, and when the reactor working volume is 3L, can produce the hydrogen of 53.3mmol every day, and the hydrogen average content reaches 42.4%.Jo-Shu Changa in 2002, Kuo-Shing Leeb, Pin-Jei Linb etc. utilizes fixed-bed bioreactor to carry out the biomass fermentation and hydrogen production test, respectively with chalina, swelling clay and gac are that the active sludge after carrier is tamed by absorption is fixed bacterial classification, are that raw material produces hydrogen continuously with sucrose, wherein are that the sorbent material effect is best with the gac, maximum hydrogen-producing speed can reach 1.21L/L.d, hydrogen content 25%-35%.Sun-Kee Han, Hang-Sik Shin etc. utilizes the filter bed reactor that food wastewater is carried out fermentation and hydrogen production, and the transformation efficiency of the COD maximum hydrogen of removal is 19.3%.KrishnanVijayaraghavan etc. utilize contact filter that jackfruit processing fruits factory waste is carried out anaerobic digestion and produce hydrogen, and hydrogen yield is the 0.72L/gVS jackfruit, and maximum hydrogen content is about 55%.Krishnan Vijayaraghavan etc. utilizes common anaerobic biological reactor, and by being that main anaerobic bacteria flora separates and tame to cow dung, obtaining maximum hydrogen content is 62%, and on average hydrogen content reaches 45.9%.In addition, domestic also have a large amount of research for biological fermentation product hydrogen reactor.The left side of Tsing-Hua University is suitable, and it is that bacterial classification carries out the experimental study that continuous anaerobe produces hydrogen with river bed mud that people such as left sword evil utilize the flow lifting type Sludge Bed of repacking voluntarily, and reactor volume is 2.6L, H
2Content is about 52.3%, and the volume of reactor produces the hydrogen rate and is up to 6.7L/L.d, and the matrix productive rate is 1.3～1.4mol/mol glucose.The maximum hydrogen-producing speed of the bio-reactor of people such as Ren Nanqi development is 10.4m
3/ m
3.d be 416mL/L.h.Above technology, for biomass fermentation and hydrogen production, the research of bio-reactor is a lot.But mostly concentrate on as cultivate bacterial classification and Primary Fermentation bio-reactor---the bio-reactor of single-stage carries out fermentation and hydrogen production, by regularly or the Continuous Flow input and output material reach the purpose of continuous product hydrogen.Since to further research of relation between desaturase and the product hydrogen, the product hydrogen utilization ratio of raw material, and the high efficiency and the stability of producing hydrogen can not realize well.
Immobilization is produced the hydrogen cell and is compared with on-fixed product hydrogen cell, and anti-low pH value is arranged, and it is long to continue the product hydrogen time, suppresses oxygen diffusion speed, prevents to produce characteristics such as hydrogen cell loss.Before this, the present patent application people proposes " a kind of immobilized microorganism and preparation method who is used for biomass fermentation and hydrogen production ", application number 200510011085.4, utilize the mixed bacterial classification of domestication to combine with carrier, fixing hydrogen-producing bacteria cell, the stability and the hydrogen-producing speed of hydrogenase in the interior cell volume of holding of reactive system and the microorganism cells are significantly increased, for lasting, stable biomass hydrogen technology provide industrialized condition.
Anaerobic biological treatment is to utilize the metabolic process of anaerobion, organism is converted into inorganics and small amounts of cells material not needing to provide under the situation of oxygen, and these inorganicss mainly are to comprise a large amount of biogas (claiming biogas Biogas) and water.Therefore, the anaerobism technology not only effectively, but also simple, and expense is cheap.
Fermentor tank of the present invention is meant with upper and lower to be conical, and the middle part tank body is columniform general biological reactor.
Summary of the invention
The objective of the invention is at desaturase and produce to concern between the hydrogen on the research basis, proposition is the method for the biomass fermentation and hydrogen production of provenance with the mixed strains immobilized microorganism, and design fermentation and hydrogen production biological reaction apparatus, improve continuously and produce hydrogen utilization ratio, high efficiency and stability with the different biomass materials of fermentation in batches.
The series-parallel connection multistage composite device of biomass fermentation and hydrogen production of the present invention has:
(1) the above fermentor tank jar row of the placed in-line successively secondary of fermentation broth stream siphunculus (18);
(2) parallel pipeline that is provided with between the 1st grade of fermentor tank (11) and 3rd level fermentor tank (13) is equipped with valve on the parallel pipeline;
(3) effuser (19) of each fermentor tank that is connected in parallel to collect hydrogen.
The above structure of the present invention has formed the series-parallel connection multistage composite device of biomass fermentation and hydrogen production purposes.
2～4 groups of spiral pipes or serpentine tube 5 are set in the described fermentor tank.
2～4 groups of spiral pipes or serpentine tube are set in the 1st～5 grade of fermentor tank, or feed water coolant, control when temperature is too high in the fermentation; Or feed steam or hot water is used for starting or low temperature season insulation.Other scale and raw materials according to design at different levels are loaded and are provided with or are provided with at interval.
Described upper and lower 1/3 place at the 1st grade of fermentor tank 11 and the 2nd grade of side fermentation jar 12 tank body height be fixed with bear mixed strains immobilized microorganism piece net every 4.
The fermentation and hydrogen production method of the series-parallel connection multistage composite device of biomass fermentation and hydrogen production comprises the immobilized microorganism that is used for biomass fermentation and hydrogen production, it is characterized in that
(1) the 1st grade of mixed strains immobilized microorganism that fermentor tank is put into desaturase enzyme activity 〉=50U/mL after taming, its weight W (ton) and tank volume V (m
3) ratio be 1%～10%, as the provenance fermenting organism reactor of cultivate holding concurrently,
It is culture medium raw material that (2) the 1st grades of fermentor tanks (11) and the 2nd grade of side fermentation jar (12) add following salt ion:
Vitriol positively charged ion M is respectively 20mg/L Fe
2+, 1mg/L Ni
2+, 100mg/L Fe
3+, 10mg/L Mg
2+, 100mg/L K
+, 1mg/L Mn
2+
The ammonium salt anion N is respectively 0.1g/L molybdate [Mo
7O
24]
6-, 1g/L oxalate [C
2O
4]
2-, 5g/L citrate [C
6H
5O
7]
3-, 1.5g/L SO
4 2-
Described side fermentation jar 12 is put into the mixed strains immobilized microorganism of desaturase enzyme activity 〉=50U/mL after taming, and its weight W is 1%～10% with the ratio of tank volume V, cultivates the fermenting organism reactor of holding concurrently as auxiliary provenance.And the pipeline valve between the 1st grade of fermentor tank (11) and the 3rd level fermentor tank (13) is opened when changing or overhauling the 2nd grade of fermentor tank (12), and all the other times then close.
The applicant has carried out following basic research before proposing the present invention:
1, with the anaerobic activated sludge is inoculum, citric acid, oxysuccinic acid, lactic acid, pyruvic acid, formic acid, oxalic acid, succsinic acid, fumaric acid, butyric acid, propionic acid and 11 kinds of organic acid fermentation and hydrogen productions of acetate have been carried out, and be inoculum after regulating anaerobic activated sludge pH value with lactic acid, having carried out stalk such as straw, cornstalk, wheat-straw, barley-straw, broad bean stalk, soya bean stalk and pig manure, cow dung, chicken manure, horsehit etc. is the research of the batch fermentation and hydrogen production of raw material.
2, study the influence factor of fermentation and hydrogen production, found out different vitriol positively charged ion M (M=20mg/L Fe
2+, 1mg/L Ni
2+, 100mg/L Fe
3+, 10mg/L Mg
2+, 100mg/L K
+, 1mg/L Mn
2+) with different ammonium salt anion Ns (N=0.1g/L molybdate [Mo
1O
24]
6-, 1g/L oxalate [C
2O
4]
2-, 5g/L citrate [C
6H
5O
7]
3-, 1.5g/L SO
4 2-) effect and combination thereof.Studies confirm that Ni
2+-Fe
3+Have to be formed with and be beneficial to the condition that the fermentation and hydrogen production process is put hydrogen, the hydrogen enzyme is carried out towards the direction that hydrogen discharge reaction takes place, thereby improved the ability of mixed bacterial fermentation and hydrogen production, also promoted the metabolism of microorganism, increased CO
2Generation.Also further confirmed molybdate [Mo
7O
24]
6---citrate [C
6H
5O
7]
3-The negatively charged ion interaction of combination has good promoter action to the metabolism that biological fermentation produces hydrogen, to promote the synergy between the mixed strains, improves the utilization and the transformation efficiency of hydrogen output and raw material.
3, applied for the patent of invention of " a kind of immobilized microorganism and preparation method who is used for biomass fermentation and hydrogen production ", application number 200510011085.4.It makes the fermentation and hydrogen production immobilized microorganism with the microorganism mixed strains, is widely used in different biomass material fermentation and hydrogen productions; Can be implemented in different sugar S (S=wood sugar, lactose, glucose, sucrose, Zulkovsky starch, potato) under the raw material, and the batch immobilized microorganism fermenting of the mixing raw material of the sucrose of hexose (simple sugar glucose), five-carbon sugar (monose wood sugar), disaccharide and lactose and polysaccharide starch is produced hydrogen.
3, set up with desaturase seed selection product hydrogen method of microorganism, successively analyzing and testing the desaturase enzyme work of flax waste water, biogas fermentation active sludge, municipal wastewater processings, percolate etc., and having carried out the research of fermentation and hydrogen production, the desaturase enzyme is lived and is become positive correlation with product hydrogen; Simultaneously be separation and the screening that index has carried out producing the hydrogen microorganism, further produce the hydrogen experiment and show with the desaturase, the desaturase enzyme lives that higher product hydrogen microorganism has that gas production rate is many, hydrogen content height in the gas, stablize and persistence good.
4, having studied the potato hydrolyzed solution is continuously ferment product hydrogen of the mixed strains immobilized microorganism of raw material, in the potato hydrolysis process, potato does not do any processing and (does not wash, do not remove the peel direct usefulness) yet, after adding the water making beating, carry out enzymic hydrolysis, drop into 7 grades and produce in the hydrogen fermentation reactor continuously, that is fresh potato → making beating → enzymic hydrolysis, → multistage fermentation and hydrogen production system → product hydrogen.Confirmed that the mixed strains immobilized microorganism is used for the potato hydrolyzed solution and continuously ferments and produce hydrogen and have efficient, continual and steady usefulness.
5, improved TTC-measuring desaturase liveness method, set up the application of desaturase aspect fermentation and hydrogen production, set up with the seed selection of desaturase enzyme activity and produced the hydrogen method of microorganism, this method has the ground introducing of the separated property of wound and is used to detect the product hydrogen evolution potential quality of used bacterial classification and the change of state parameter situation of monitoring fermenting process.Successively analyzing and testing the desaturase enzyme work of flax waste water, biogas fermentation active sludge, municipal wastewater processings, percolate etc.The minimum dehydrogenase activity level of mixed strains of being used for fixing has been understood in research, further produces the hydrogen experiment and shows, the desaturase enzyme lives that higher product hydrogen microorganism has that gas production rate is many, hydrogen content height in the gas, stablize and persistence good.
Desaturase enzyme activity unit (U) definition: with TCC TTC (2,3,5-triphenyltetrazolium) be substrate, sample and substrate be at 40 ℃ of following isothermal reaction 2h, and the amount (μ gTPF/mL h) of the 1 μ g first hairpin TPF (triphenylformazan) that generates in 1h with 1mL or 1g sample is defined as an enzyme activity unit U.
The measuring method process of dehydrogenase activity: get 2mL sample liquid suspensions, adding 1mL 0.5%TTC solution (its empty replaces TTC solution with 1mL distilled water) vibration shakes up, boil 10min behind 40 ℃ of water-bath 2h, adding the saturated NaCl solution of 1mL mixes, cooling adds extraction agent acetone 3mL again and mixes, leave standstill 5min, add the extraction of 5mL toluene.To extract supernatant liquor and move in the 1cm cuvette, on 721 spectrophotometers, measure OD
490nmValue.To measure OD
490nmValue is looked into the amount that typical curve is found out corresponding TPF, calculates the dehydrogenase activity (enzyme activity unit) of institute's test sample product by following formula:
DHA(U)＝(m·B)/(A·C)
B-surveys OD
490nmThe TPF value that value is found from typical curve, μ g.
The reaction volume of A-sample, mL.
M-diluted sample multiple,
The C-insulation reaction time, 2h
The DHA-dehydrogenase activity, the U=μ gTPE/h.mL of unit
6, be to investigate comprehensively and analyze understanding hydrogen net production and desaturase enzyme relation alive, the production index of 81 hydrogen is divided into three groups after with series arrangement from small to large, the result value that the desaturase enzyme of the corresponding experiment of hydrogen output in every group number is lived also is included into respectively not on the same group, adopt the single-factor statistical analysis technique, to the variance statistical results show between desaturase and hydrogen output group: F
ABe 3.18, greater than F
0.05(2,78)=3.113 are less than F
0.01(2,78)=4.888 prove that there are significant positive correlation in the net production of hydrogen and the work of desaturase enzyme, and promptly the desaturase enzyme is lived and just directly reflected the height of hydrogen output.
7, studied the dynamic change of desaturase enzyme work in immobilization batch fermentation and hydrogen production process, with the directly related index of fermentation and hydrogen production, hydrogen output, hydrogen-producing speed, residual sugar content, analyzed and the dynamic rule of desaturase enzyme work in mixed strains immobilized microorganism fermenting product hydrogen process, drawn:
(1), the mixed strains immobilized microorganism that the microorganism of desaturase enzyme activity 〉=50U/mL is made after taming, with the potato hydrolyzed solution is the batch fermentation and hydrogen production that raw material carries out, be 12h start time, total hydrogen output reaches 7.14L, carried out altogether 74 hours from start to product hydrogen end (being as the criterion less than hydrogen to detect) in fermentor tank, hydrogen yield is up to 2.60mol/moL glucose.
(2), desaturase enzyme output alive and hydrogen characterizes out opposite variation tendency over time in the whole product hydrogen process system, that is to say when hydrogen output is zero or hangs down, mixing microorganisms carries out a large amount of dehydrogenation reactions to raw material or intermediate metabolites, thereby (ferredoxin) provides more electronics to ferredoxin, so that discharge hydrogen by the re-oxidation of hydrogenase.Illustrate further: the dehydrogenation reaction of desaturase is that the first step of biomass fermentation and hydrogen production also is an important step.
(3) this research by to the dynamic changing process of whole biomass fermentation and hydrogen production to the desaturase enzyme work follow the tracks of detection, preliminary study the variation relation that produces of desaturase and hydrogen.Confirmed that desaturase and the growth and decline of producing hydrogen present alternately rule.In view of the above, if adopt multistage continuously fermenting,, just may remedy the follow-up weak defective of fermentation in batches to adapt to desaturase and the alternately rule of producing hydrogen.
The present invention utilizes common fermentor tank series-parallel connection to constitute the fermentation and hydrogen production device, can utilize existing equipment, and cost is low, implements easily.
The present invention explore product hydrogen suitable condition influence bacterial classification and flora, research from the processing organic waste to directly utilizing native starch, Mierocrystalline cellulose to produce on a large scale on the development priority biomass fermentation and hydrogen production basis of hydrogen, adapted to desaturase and produced the rule that hydrogen alternately occurs with the multistage hydrogen production bioreactor that continuously ferments, solve the single-stage bio-reactor and produced hydrogen for one thing cited, ten thousand may have been left out follow-up weak defective, fully improve the product hydrogen utilization ratio of raw material, realized producing high efficiency, the continuous stability of hydrogen.
Description of drawings
The multistage fermentor device of plant-scale fermentation and hydrogen production and the connecting process schematic drawing of Fig. 1, design.Number in the figure is:
1, immobilized microorganism is imported and exported; 2, manhole; 3, mixed strains immobilized microorganism; 4, sieve plate; 5, spiral or sinuous coil; 6, sewage draining exit; 7, expand spheroid; 8, access hole; 9, thief hole; 10, direct opening for feed; 11, the 1st grade of fermentor tank; 12, the 2nd grade of fermentor tank; 13,3rd level fermentor tank; 14, the 4th～n level fermentor tank; 15, CO
2Removal device; 16, O
2Removal device; 17, H
2Gas storage device.18, fermentation broth stream siphunculus and channel valve; 19, effuser
The experiment type fermentation and hydrogen production fermentor device of Fig. 2,1L.
Fig. 3, be 7 cascade supervention ferment process flow sheets of raw material with the potato hydrolyzed solution.
Embodiment
Embodiment 1:
Among Fig. 1,2, with the experiment type fermentation and hydrogen production fermentor device of 1L, with 7 grades of series connection of fermentor tank, only the 1st grade is dropped into mixed strains immobilized microorganism piece 50～100g.Do not drop into the immobilized microorganism piece in placed in-line other fermentation and hydrogen production fermentor tanks at different levels.From the 1st grade of opening for feed regularly, quantitatively add the potato hydrolyzed solution, enter from the 2nd grade of opening for feed, be operated to last step so in regular turn and carry out fermentation and hydrogen production from the same volume of discharge port sucking-off.The gas volumes of measuring respectively at different levels, hydrogen content, and relevant index of sampling analysis and desaturase enzyme activity.
The 1st grade, the ability of mixed strains immobilized microorganism provenance is investigated
From starting the preceding 14h of beginning, desaturase work is in a higher relatively level, and this moment, hydrogen did not almost produce; Along with the generation of hydrogen, desaturase work is for a relatively low level behind the 14h, a small peak just appears again behind 40h and this moment hydrogen output drop to 141mL by maximum production 1068mL.The net production of hydrogen always is the variation of alternative rule with the variation that desaturase is lived in whole dynamic process, and when desaturase work was in crest, the net production of hydrogen always was in trough; And when desaturase work was in trough, the net production of hydrogen then all was to be in crest usually.And in the dynamic changing process of whole fermentation and hydrogen production always when desaturase work is in higher level, its, hydrogen output was also higher in period in subsequently corresponding next.Proof: by the leading dehydrogenation reaction of desaturase is that the first step of biomass fermentation and hydrogen production also is a most important step, and the generation of itself and hydrogen has close getting in touch; The height that fermentation and hydrogen production process desaturase is lived is an important index, and it has directly influenced the output of follow-up hydrogen.
Single batch is produced hydrogen evolution potential: 118.1mL/g potato dry weight is equivalent to 1.07moL/moL glucose.
Embodiment 2: after 1 fermentation period of the 1st grade of provenance of single batch of investigation met the requirement of expection, formally starting multistage fermentor tank placed in-line was the product hydrogen that continuously ferments of raw material with the potato hydrolyzed solution.
Among Fig. 1,3, the 1st grade (11) cultivate the fermentor tank of holding concurrently fermentation for provenance, and the 2nd grade (12) cultivate the side fermentation jar of holding concurrently fermentation for auxiliary provenance.This two-stage fermentation jar welds upper and lower 2 sieve plates of system with the reinforcing bar of diameter 〉=1.5cm about crisscross spacing 10cm, plate is located at upper and lower about 1/3 place of tank body height respectively.Between two plates for catching mixed strains immobilized microorganism species block space.Upper plate leaves the 90cm square hole that is used to put into, take out the immobilization piece.
Pipeline is provided with valve between the fermentor tank in twos.The top of fermentor tanks at different levels is a pneumatic outlet, gas through a caliber be 3 times of normal calibers expand spherule 7, fermented liquid and the foam taken out of are fallen after rise in the reactor.Gas can enter CO by T-valve control
2Removal device (15) enters O again
2Removal device (16) is handled, last pure H
2Enter gas storage device (17); Also can handle respectively.Each reactor bottom is emissions such as the fermentation precipitation outlet by valve control, but the high low composting material of entered biogas fermentation, water content of water content.
In the 1st grade of fermentor tank and the 2nd grade of side fermentation jar, put into the mixed strains immobilized microorganism species of 6% (weight W/tank volume V) respectively, this bacterial classification adopts the preparation of " a kind of immobilized microorganism and preparation method who is used for biomass fermentation and hydrogen production " patent application (application number 200510011085.4) method, the kind amount of immobilized microorganism species is in weight t, and the fermentor tank volume is with m
3Meter.In the substratum of mixed strains immobilized microorganism, add vitriol positively charged ion M (M=20mg/L Fe
2+, 1mg/L Ni
2+, 100mg/LFe
3+, 10mg/L Mg
2+, 100mg/L K
+, 1mg/L Mn
2+) and ammonium salt anion N (N=0.1g/L molybdate [Mo
7O
24]
6-, 1g/L oxalate [C
2O
4]
2-, 5g/L citrate [C
6H
5O
7]
3-, 1.5g/L SO
4 2-).Deployed raw material can be added by top stream from 1,2 grade of opening for feed and enters, and following of normal circumstances adds from the 1st grade of opening for feed stream and enters.In starting, maintenance with when changing Special Circumstances such as bacterial classification, respectively simultaneously or enter separately by the 1st, 2.When changing the 1st grade of bacterial classification or maintenance, the pipeline of closing between 1,2 and 1,3 connects valve, provides provenance by normal conveying of 2,3 pipelines; Change or when overhauling the 2nd grade, open 1,3 parallel tubess and carry provenance is provided.1, generally closes under the 3 parallel tubes normal circumstancess.
The immobilized microorganism provenance pieces of not putting at different levels after the 3rd level (13), incoming stock for not adding the rough raw material of inorganic salt M, N, only control loads such as sugared concentration or COD.The liquid stream of fermented liquid goes into for unpowered to flow to the next stage spontaneous current in turn.
The 1st grade, desaturase always keeps higher enzyme activity 163.01 U, H
2Content is low by 35～40%, CO
2Content is higher;
The 2nd grade, desaturase enzyme activity 66.49U is than the 1st grade of decline, H
2Content is high than the 1st grade, CO
2Content is than the 1st grade low about 5%;
3rd level, in 7 grades of series connection systems, desaturase highest level enzyme activity 1427.27 U appear in this level, this grade desaturase enzyme activity, H
2Content, CO
2Content is to change and the maximum that fluctuates;
The 4th grade, each index of this level changes more steady, desaturase enzyme activity 69.98U, H
2Content and CO
2Content respectively is half;
The 5th grade, in 7 grades of series connection systems, except that the 7th grade, the desaturase enzyme activity 19.43U of this grade is minimum in the system, H
2Content reaches as high as more than 85%, CO
2Content is minimum;
The 6th grade, H steadily enzyme activity rising phenomenon often appears not, in desaturase and the 5th grade of comparison
2Content drops to about 65%, CO
2Content also raises;
The 7th grade, almost consumed to the 6th grade of raw material, in the 7th grade, have only less gas to produce, the desaturase enzyme activity is generally 3.28U, H
2Content 16.28%, CO
2Content higher 82.14%.
More than in 7 grades of fermentations, the H at different levels respectively
2Content, H
2Generation, and the dehydrogenase activity variation is greatly, but with regard to whole system, the total gas production of every day and total hydrogen generating quantity do not have marked difference on amount.Investigate desaturase enzyme activity, H with the fixed time actual measurement
2Content difference at different levels is very big, but does not have marked difference between the mean value in the different moment.With the product hydrogen that continuously ferments of this multilevel device, the defective that has remedied the charging of single stage system Continuous Flow or fermented in batches, the while has been held both advantages again.
The system of continuously fermenting of this 7 stage arrangement, the 80d that ferments altogether, shared fresh potato 14400g amounts to dry weight 3577.2g with TS, and dry weight yam starch content is 89%, is equivalent to 1g glucose meter, gross output H with the amount of 1g starch
2Potentiality are 303.89mL/g glucose, are equivalent to 2.286moLH
2/ moL glucose, maximum hydrogen-producing speed are 450mL/L.h, that is: 10.8L/L.d;
The starting phase exceeds with the 7th grade of full fermented liquid of stream, is the normal fermentation stage of stable development to be total to 75d, stage of stable development gross output H afterwards
2The glucose of potentiality 386.0mL/g potato is equivalent to 3.10moLH
2/ moL glucose, the end result who stops incoming stock collection residual air is not counted in during this.
The hydrogen output of system operation 80d has improved 70% than the 1st grade of single reaction vessel investigation value in batches; Improved 91.0% with regard to regard to the stage of stable development, investigating the hydrogen output value in batches than the 1st grade of single reaction vessel.Presentation of results device of the present invention multistage continuously and multiple technologies technology composite design reasonable, can be efficiently, lasting, fermentation and hydrogen production stably, obviously improved the product hydrogen utilization ratio of raw material.
The present invention is suitable with a domestic Tsing-Hua University left side, and the people such as left sword evil utilize the up-flow mud sheet of repacking take river bed mud as bacterial classification One reactor, the long period that Continuous Flow turnover glucose feed liquid is carried out produces continuously hydrogen and compares. The average product hydrogen of 80d of the present invention is 2.286moLH2/ moL glucose, suitable with a left side, the high yield hydrogen 1.4mol/mol glucose of left sword evil etc. is compared and has been improved 63.3%.
Claims (6)
1, the series-parallel connection multistage composite device of biomass fermentation and hydrogen production is characterized in that this device has:
(1) the above fermentor tank jar row of the placed in-line successively secondary of fermentation broth stream siphunculus (18);
(2) between the 1st grade of fermentor tank (11) and 3rd level fermentor tank (13), link, and the 1st grade of fermentor tank (11) and the 2nd grade of side fermentation jar (12) link with the pipeline that valve is set too, form the series-parallel connection combination with the pipeline that valve is set;
(3) effuser (19) of each fermentor tank that is connected in parallel to collect hydrogen.
2, the series-parallel connection multistage composite device of biomass fermentation and hydrogen production according to claim 1 is characterized in that being provided with 2～4 groups of spiral pipes or serpentine tube (5) in fermentor tank.
3, the series-parallel connection multistage composite device of biomass fermentation and hydrogen production according to claim 1, it is characterized in that being fixed with at upper and lower 1/3 place of the 1st grade of fermentor tank (11) and the 2nd grade of side fermentation jar (12) tank body height bear mixed strains immobilized microorganism piece net every (4).
4, the fermentation and hydrogen production method of the series-parallel connection multistage composite device of biomass fermentation and hydrogen production comprises the immobilized microorganism that is used for biomass fermentation and hydrogen production, it is characterized in that:
(1) the 1st grade of mixed strains immobilized microorganism that fermentor tank is put into desaturase enzyme activity 〉=50U/mL after taming, its weight W ton and tank volume Vm
3Ratio be 1%～10%, as the provenance fermenting organism reactor of cultivate holding concurrently;
It is culture medium raw material that (2) the 1st grades of fermentor tanks (11) and the 2nd grade of side fermentation jar (12) add following salt ion:
Vitriol positively charged ion M is respectively 20mg/L Fe
2+, 1mg/L Ni
2+, 100mg/L Fe
2+, 10mg/L Mg
2+, 100mg/L K
+, 1mg/L Mn
2+,
The ammonium salt anion N is respectively 0.1g/L molybdate [Mo
7O
24]
6-, 1g/L oxalate [C
2O
4]
2-, 5g/L citrate [C
6H
5O
7]
3-, 1.5g/L SO
4 2-
(3) to flow to the next stage fermentor tank by fermented liquid pipe (18) from the upper level fermentor tank be advancing naturally of unpowered supply to biomass material.
5, fermentation and hydrogen production method according to claim 4, it is characterized in that the 2nd grade of side fermentation jar (12) put into the mixed strains immobilized microorganism of desaturase enzyme activity 〉=50U/mL after taming, its weight W is 1%～10% with the ratio of tank volume V, cultivates the fermenting organism reactor of holding concurrently as auxiliary provenance.
6, fermentation and hydrogen production method according to claim 4 is characterized in that the pipeline valve between the 1st grade of fermentor tank (11) and the 3rd level fermentor tank (13) is opened when changing or overhauling the 2nd grade of fermentor tank (12), all the other times then close.
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| CN107254408A (en) * | 2017-06-28 | 2017-10-17 | 耐可苏（武汉）生物科技有限公司 | A kind of compound biological enzyme mineral activated solution circulating fermentation process and device |
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