CN107761126A

CN107761126A - A kind of microorganism electrolysis cell hydrogen manufacturing liquid

Info

Publication number: CN107761126A
Application number: CN201610678659.1A
Authority: CN
Inventors: 黄增才
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-08-17
Filing date: 2016-08-17
Publication date: 2018-03-06

Abstract

The present invention discloses a kind of microorganism electrolysis cell hydrogen manufacturing liquid, and nitrogen is full of into industrial wastewater, is fermented with acetogen, and adjustment zymotic fluid pH value is 7, C/N 44, adds second bromoethane sulfonic acid salt 20mmol/L, adds 1mL/L nutrient solutions.The present invention is by optimizing pH value, C/N and second bromoethane sulfonic acid salinity, realize in hydrogen manufacturing liquid that acetic acid, lactic acid, propionic acid and butyric acid density respectively reach 1031.12 mg/L, 51.32 mg/L, 84.94 mg/L, 71.24 mg/L, while to the clearance of COD in industrial wastewater up to 99%.

Description

A kind of microorganism electrolysis cell hydrogen manufacturing liquid

Technical field

It the present invention relates to the use of electricity generation by microorganism technology, and in particular to hydrogen manufacturing liquid.

Background technology

Microorganism electrolysis cell（Microbial electrolysis cell, MEC）, one kind as newly-developed can use In weaken anaerobism " fermentation obstacle " phenomenon hydrogen producing technology in recent years by the extensive attention of domestic and international researcher.By biological electricity Catalysis technique, using organic wastewater as electron donor, the electroactive microbial degradation substrate adhered to by anode discharges electronics and matter Son, and electronics is received so as to produce H by proton in negative electrode₂.When organic matter by pyruvate pathway be metabolized generation acetic acid, propionic acid and After the aliphatic acid such as butyric acid, under the driving of the two poles of the earth auxiliary voltage, can will fermentation end productses further degrade and discharge proton and Electronics, so as to increase substantially H₂Yield.Influence the setting of the principal element including extra voltage of MEC production hydrogen efficiency, substrate Selection, selected and cathod catalyst the determination of electrode material.

Course of reaction is mainly completed by the chemical reaction at the two poles of the earth, wherein using acetic acid as the course of reaction such as formula of substrate （1）, formula（2）It is shown.

Anode：CH₃COOH+2H₂O→CO₂+8H⁺+8e⁻（1）

Negative electrode：8H⁺+8e⁻→4H2 （2）

According to Nernst equation, when pH values are 7.0, negative electrode, which produces hydrogen, at least needs 410 mV potential, and traditional Potential caused by MEC loops typically in 300 mV or so, so, for obtain hydrogen, add the interpolar of negative and positive two voltage extremely Less in 110mV.In actual MEC runnings, it is contemplated that the influence of internal resistance, be normally set up magnitude of voltage 0.2~0.8 V it Between.

Select suitable substrate then most important to development MEC process for making hydrogen, it will directly determine the cost of process operation And hydrogen yield.In MEC, when complex carbohydrates are after hydrolysis generates monose, microorganism passes through sugar under anaerobic Monose glycolysis is pyruvic acid by diphosphate pathway, then balances coenzyme NAD by the redox machinery of pyruvic acid⁺Or NADP⁺'s Amount, the metabolism production capacity process of microorganism is maintained, gone on so that reaction is spontaneous.After pyruvate oxidation reduction, produce The end productses such as volatile fatty acid such as acetic acid, propionic acid, butyric acid, under the driving of extra voltage, oxygen can be continued by microorganism Change, so as to realize the decrease of anaerobism " fermentation obstacle " phenomenon.

Currently, carried out with formates, sodium acetate, waste water of livestock poultry, fermentation water outlet, industrial wastewater, protein and glucose Hydrogen research is produced Deng MEC is carried out for substrate.For different substrate types, due to sodium acetate can be directly entered biochemical reaction so as to Hydrogen outputs more more than compound protein etc. can be obtained.

The content of the invention

In consideration of it, present invention aims at provide a kind of hydrogen generation efficiency higher microorganism electrolysis cell hydrogen manufacturing liquid.

To solve above technical problem, technical scheme provided by the invention is to provide a kind of microorganism electrolysis cell hydrogen manufacturing liquid, Nitrogen is full of into industrial wastewater, is fermented with acetogen, adjustment zymotic fluid pH value is 7, C/N 44, adds second bromoethane sulphur Hydrochlorate 20mmol/L, add 1mL/L nutrient solutions.

Preferably, the acetogen is acetobacter.

Preferably, the composition of the nutrient solution is as follows：H₃BO₃50mg/L, CuCl₂30mg/L, MnSO₄·H₂O50mg/L, (NH₄)₆Mo₇O₂₄·4H₂O50mg/L, AlCl₃50mg/L, CoCl₂·6H₂O50mg/L, NiCl₂50mg/L, ZnCl₂50mg/L。

Compared with prior art, a technical scheme in above-mentioned technical proposal has the following advantages that：

1st, the present invention realizes high acetic acid producing rate by optimizing pH value, C/N and second bromoethane sulfonic acid salinity.Second bromoethane sulfonic acid Salt does not influence in addition to methanogen on other anaerobic acid-production bacteriums, under concentration of the present invention, can suppress thermophilic producing hydrogen and methane bacterium and Thermophilic acetic acid and methane producing bacterium, and the growth of homoacetogenic bacteria can be promoted, acid and homoacetogenesis process are produced come real by hydrolysed ferment The accumulation of acetic acid concentration in existing anaerobic fermentation end productses.

2nd, acetic acid, lactic acid, propionic acid and butyric acid density are respectively in hydrogen manufacturing liquid of the present invention：1031.12 mg/L、 51.32 mg/L、84.94 mg/L、71.24 mg/L。

Embodiment

Nitrogen is full of into industrial wastewater, entering acetobacter with acetogen is fermented, and inflated with nitrogen is advantageously reduced in waste water Oxygen content, ensure that industrial wastewater is in anaerobic state, feed them into anaerobic hydrogen-generating pattern.Adjusted and sent out using phosphate buffer Zymotic fluid pH value is 7, and carbon, nitrogen ratio are 44 in adjustment waste water, and add second bromoethane sulfonic acid salt according to 20mmol/L, according to 1mL/L Nutrient solution is added, obtains hydrogen manufacturing liquid.The composition of nutrient solution is as follows：H₃BO₃50mg/L, CuCl₂30mg/L, MnSO₄·H₂O50mg/L, (NH₄)₆Mo₇O₂₄·4H₂O50mg/L, AlCl₃50mg/L, CoCl₂·6H₂O50mg/L, NiCl₂50mg/L, ZnCl₂50mg/L。

Acetic acid, lactic acid, propionic acid and butyric acid density are respectively in hydrogen manufacturing liquid of the present invention：1031.12 mg/L、 51.32 mg/ L、84.94 mg/L、71.24 mg/L。

It is substrate using anaerobic fermentation preparation of hydrogen waste liquid, using acetic acid as main electron donor, in electrolytic cell reactor, with The stainless (steel) wire for being coated with Ni nano particles is negative electrode, and carbon cloth is anode, can finally obtain 1.32m³H₂/(m³D) and 2.8mLH₂/ mgCOD production hydrogen rate, and 138% energy efficiency, while to the clearance of COD in industrial wastewater up to 99 %。

Claims

A kind of 1. microorganism electrolysis cell hydrogen manufacturing liquid, it is characterised in that nitrogen is full of into industrial wastewater, is fermented with acetogen, It is 7, C/N 44 to adjust zymotic fluid pH value, adds second bromoethane sulfonic acid salt 20mmol/L, adds 1mL/L nutrient solutions, the production second Sour bacterium is acetobacter, and the composition of the nutrient solution is as follows：H₃BO₃50mg/L, CuCl₂30mg/L, MnSO₄·H₂O50mg/L, (NH₄)₆Mo₇O₂₄·4H₂O50mg/L, AlCl₃50mg/L, CoCl₂·6H₂O50mg/L, NiCl₂50mg/L, ZnCl₂50mg/L。