Effects of Acetic and Formic Acid on ABE Production by Clostridium acetobutylicum and Clostridium beijerinckii

조대행,Soo-Jeong Shin,김용환 한국생물공학회 2012 Biotechnology and Bioprocess Engineering Vol.17 No.2

The effect of acetic acid and formic acid on acetone-butanol-ethanol (ABE) production by solventogenic Clostridia was investigated. The ABE concentration in Clostridium acetobutylicum was found to have increased slightly on addition of 3.7 ~ 9.7 g/L acetic acid, but was found to have drastically reduced in the presence of 11.7g/L acetic acid. However, the solvent production of C. beijerinckii was not affected by addition of acetic acid in the range of 3.7 ~ 11.7 g/L. C. acetobutylicum was more vulnerable to formic acid than C. beijerinckii. In C. acetobutylicum, the total ABE production decreased to 77% on addition of 0.4 g/L formic acid and 25% with 1.0g/L formic acid. The total ABE production by C. acetobutylicum was also noted to have decreased from 15.1to 8.6 g/L when 8.7 g/L acetic acid and 0.4 g/L formic acid co-existed. The solvent production by C. beijerinckii was not affected at all under the tested concentration range of formic acid (0.0 ~ 1.0 g/L) and co-presence of acetic acid and formic acid. Therefore, C. beijerinckii is more favorable than C. acetobutylicum when the ABE is produced using lignocellulosic hydrolysate containing acetic and formic acid.

공업화학,촉매/반응공학 : 고농도 질산 분해를 위한 연속식 화학-전해 조합 탈질 공정 (1)

김광욱 ( Kim Gwang Ug ),김수호 ( Kim Su Ho ),이일희 ( Lee Il Hui ) 한국화학공학회 2004 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.42 No.1

This work has improved the conventional batch denitration by formic acid which has been used for controlling the acidity of solution for the solvent extractions to partition the long lived-radionuclides from the high level radioactive liquid waste. The characteristics of destructions of nitric acid and formic acid and their destructive products in a continuous denitration process combining a continuous denitration system by formic acid and an electrolytic residual acid-trimming system suggested in this work was evaluated. The continuous denitration by formic acid reached a steady state in 30 minutes and showed the dependence of the final acidity on the residence time of feeding solution into the reactor. Also the system had the lowest final acidity at a mole ratio of formic acid and nitric acid of 1.5 like the batch denitration. In a Ti-IrO₂ electrolytic cell, the destructive rates of formic acid and nitric acid were 9.33×10^(-3) and 10^(-2)/M(hr·mA/㎠), respectively. The nitric acid and the formic acid were destructed through the reduction at the T₁ cathode and the oxidation at the IrO₂ anode, respectively. The newly suggested continuous denitration process combining the denitation by formic acid and residual acid-electrolytic treatment could control continuously a feeding nitric acid of 2.0M to below about 0.1M.

n-Propanol과 Formic acid계의 최소자연발화온도의 측정

조영세,하동명 한국화재소방학회 2013 한국화재소방학회논문지 Vol.27 No.5

The autoignition temperatures (AITs) of solvent mixture was important index for the safe handling of flammable liquids which constitute the solvent mixtures. This study measured the AITs and ignition delay time for n-propanol and formic acid system by using ASTM E659 apparatus. The AITs of n-Propanol and Formic acid which constituted binary system were 435 oC and 498 oC, respectively. The experimental AITs of n-propanol and formic acid system were a good agreement with the calculated AITs by the proposed equations with a few A.A.D. (average absolute deviation). And n-Propanol and formic acid system was shown the minimum autoignition temperature behavior (MAITB). 가연성 혼합물의 최소자연발화온도는 가연성액체의 안전한 취급을 위해서 중요한 지표가 된다. 본 연구에서는 ASTM E659 장치를 이용하여 가연성 혼합물인 n-Propanol과 Formic acid 계의 최소자연발화온도와 발화지연시간을 측정하였다. 2성분계를 구성하는 순수물질인 n-Propanol과 Formic acid의 최소자연발화온도는 각 각 435 oC와 498 oC로 측정되었다. 그리고 측정된 n-Propanol과 Formic acid 계의 최소자연발화온도는 제시된 식에 의한 예측값과 작은 평균절대오차에서 일치하였다. 그리고 n-Propanol과 Formic acid 계는 일부 혼합 조성에서 두 개의 순수물질 가운데 낮은 AIT보다낮게 측정된 최소자연발화온도거동(MAITB, Minimum Autoignition Temperature Behavior)을 보이고 있다.

전해적 잔여 산 처리를 동반한 개미산 가속 탈질

김광국 ( Kwang Wook Kim ),김수호 ( Soo Ho Kim ),이일희 ( Eil Hee Lee ) 한국공업화학회 2002 공업화학 Vol.13 No.7

지금까지의 소멸처리를 위한 군분리 공정에서 질산의 산도 조절은 개미산에 의한 탈질 방법이 사용되어 왔으나 이 방법으로는 최종 산도를 0.5 M이하로 낮출 수 없고 반응 시간이 길어 공정을 연속화하는데 문제를 가지고 있다. 본 연구에서는 기존의 개미산 탈질 공정을 개선하기 위하여 기본에 사용하는 질산에 대한 개미산의 몰 비율인 1.5 보다 높은 2.0 이상을 사용하여 빠른 질산 분해를 수행한 후 촉매성 산화물 전극에 의해 잔여 개미산의 분해 및 질산의 분해를 통해 신속히 산을 분해 처리하는 가속 개미산 탈질- 전해 trimming 공정의 조합 공정을 제시하였다. 여기서는 질산에 대한 개미산의 몰 비를 2.0 이상으로 하여 질산농도를 1 h 내에 2.0에서 0.5 M 이하로 신속히 낮추고, 이후 그 용액을 80∼100 mA/㎠이 공급되는 촉매성 산화물 전극을 갖는 셀 2∼3개를 사용하여 30∼60 min 내에 잔여 개미산을 1.0 M 그리고 질산은 0.3 M 이상을 분해 하여 최종 총 산도를 0.3∼0.4 M 이하로 낮출 수 있었다. 이러한 결과로부터 개미산에 의한 탈질을 연속식으로 조업할 수 있음을 확인하였다. Controlling the acidity of nitric acid in the partitioning process for transmutation has been carried out by denitration with formic acid. However, using this method, the final acidity cannot go down below 0.5 M, and it takes a long time to reach the equilibrium. For these reasons, the conventional denitration with formic acid process is not utilized in a continuous operation of the partitioning process. In this work, a new process concept of accelerated denitration with formic acid-electrolytic trimming of residual acidity was suggested. In this new method, mole ratio of formic acid to nitric acid was kept at higher than 2.0 for the denitration rather than the fixed ratio of 1.5 used in the conventional denitration. This helped to reduce 2.0 M nitric acid to less than 0.5 M withins 1 h. With the electrolytic treatment of the solution by using 2∼3 cells of catalytic oxide electrodes at 80∼100 mA/㎠ for 30∼60 min, the feeding solution of 2.0 M nitric acid was reduced to 0.3∼0.4 M in the final effluent. Thus with the new treatments, the denitration with formic acid can be adopted in the continuous operation.

Optimal design and experimental validation of a simulated moving bed chromatography for continuous recovery of formic acid in a model mixture of three organic acids from Actinobacillus bacteria fermentation

Park, C.,Nam, H.G.,Lee, K.B.,Mun, S. Elsevier 2014 Journal of chromatography Vol.1365 No.-

The economically-efficient separation of formic acid from acetic acid and succinic acid has been a key issue in the production of formic acid with the Actinobacillus bacteria fermentation. To address this issue, an optimal three-zone simulated moving bed (SMB) chromatography for continuous separation of formic acid from acetic acid and succinic acid was developed in this study. As a first step for this task, the adsorption isotherm and mass-transfer parameters of each organic acid on the qualified adsorbent (Amberchrom-CG300C) were determined through a series of multiple frontal experiments. The determined parameters were then used in optimizing the SMB process for the considered separation. During such optimization, the additional investigation for selecting a proper SMB port configuration, which could be more advantageous for attaining better process performances, was carried out between two possible configurations. It was found that if the properly selected port configuration was adopted in the SMB of interest, the throughout and the formic-acid product concentration could be increased by 82% and 181% respectively. Finally, the optimized SMB process based on the properly selected port configuration was tested experimentally using a self-assembled SMB unit with three zones. The SMB experimental results and the relevant computer simulation verified that the developed process in this study was successful in continuous recovery of formic acid from a ternary organic-acid mixture of interest with high throughput, high purity, high yield, and high product concentration.

공업화학,촉매/반응공학 : 금속 이온의 침전이 동반되는 연속식 화학-전해 조합 탈질 공정 특성 (2)

김광욱 ( Kim Gwang Ug ),김수호 ( Kim Su Ho ),이일희 ( Lee Il Hui ) 한국화학공학회 2004 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.42 No.1

This work has studied the characteristics of destruction of nitric acid and precipitation of several metal ions in a continuous denitration process combining by formic acid and a residual acid-electrolytic trimming system. The process could treat continuously and effectively a feeding nitric acid of 2.0M to below about 0.1M. The metal ions of Zr, Mo, Fe, and Nd did not affect the electrodes at the step of electrolytic trimming of the residual acid after denitration by formic acid. The Mo ion in electrolytic solution enhanced the generation of nitrite ion during the electrolytic reaction. The mole ratio of formic acid to nitric acid fed into the continuous denitration reactor using formic acid affected much the final acidity, the precipitation yields of metal ions, the precipitate morphology. At the ratio of 1.65, the process had the lowest final acidity of less than 0.1M, and the precipitation yields of Zr and Mo reached 95% and 83%, respectively as the highest values. Only the precipitate generated in the mole ratio of formic acid to nitric acid between 1.5 and 1.7 had a needle-shaped morphology, otherwise it was granular-shaped.

Research Articles : Proteomic Evaluation of Cellular Responses of Saccharomyces cerevisiae to Formic Acid Stress

( Sung Eun Lee ),( Byeoung Soo Park ),( Jeong Jun Yoon ) 한국균학회 2010 Mycobiology Vol.38 No.4

Formic acid is a representative carboxylic acid that inhibits bacterial cell growth, and thus it is generally considered to constitute an obstacle to the reuse of renewable biomass. In this study, Saccharomyces cerevisiae was used to elucidate changes in protein levels in response to formic acid. Fifty-seven differentially expressed proteins in response to formic acid toxicity in S. cerevisiae were identified by 1D-PAGE and nano-liquid chromatography-tandem mass spectrometry (nano-LC-MS/MS) analyses. Among the 28 proteins increased in expression, four were involved in the MAP kinase signal transduction pathway and one in the oxidative stress-induced pathway. A dramatic increase was observed in the number of ion transporters related to maintenance of acid-base balance. Regarding the 29 proteins decreased in expression, they were found to participate in transcription during cell division. Heat shock protein 70, glutathione reductase, and cytochrome c oxidase were measured by LC-MS/MS analysis. Taken together, the inhibitory action of formic acid on S. cerevisiae cells might disrupt the acidbase balance across the cell membrane and generate oxidative stress, leading to repressed cell division and death. S. cerevisiae also induced expression of ion transporters, which may be required to maintain the acid-base balance when yeast cells are exposed to high concentrations of formic acid in growth medium.

The effect of hemicelluloses and lignin on acid hydrolysis of cellulose

Yoon, S.Y.,Han, S.H.,Shin, S.J. Pergamon Press 2014 ENERGY Vol.77 No.-

In acid hydrolysis of plant biomass, polysaccharides are converted to monosaccharides, which is basic raw material for biorefinery for fermentation based process. These monosaccharides, however, are not stable in acidic reaction medium, and are converted to organic acids via furans. Impact of hemicelluloses and lignin on acid hydrolysis of cellulose was investigated to focus on monosaccharide production with different degrees of cellulose purity. Two-step concentrated sulphuric acid process was applied to biomass for monosaccharide conversion. Kinetics of cellulose hydrolysis was analysed using <SUP>1</SUP>H NMR spectroscopy. Higher reaction temperature in secondary hydrolysis caused severe degradation of the monosaccharides. In pure and holocellulose, further reaction of glucose in acidic reaction medium produced formic acid and levulinic acid. However, lignocellulosic biomass generated much less formic acid and levulinic acid under the same reaction condition. Humin (or pseudo-lignin) was also formed by the condensation of lignin and furans from monosaccharides in acidic reaction condition. Thus, the fermentation inhibitors, furans and formic acid, were generated in low quantities by lignocellulosic biomass than by delignified biomass such as pure cellulose or holocellulose.

Sensing formic acid with a water-based chitosan lanthanide luminescence film

Xu Zheng,Xi Chen,Xudong Yu,Yifan Yang 한국공업화학회 2023 Journal of Industrial and Engineering Chemistry Vol.125 No.-

A sensitive and selective formic acid sensor could be useful in detecting this corrosive acid in industrial,medical, and environmental settings. Herein, we present a film for detection of formic acid. We introducedchitosan as a film-forming factor to creatively overcome the problem that chitosan dissolves inacids. A carboxylic acid-carbon dot solution was used to replace the strong acid solution and prepare aluminescent film in which the color changed from green to blue when it was exposed to formic acid. Integrated data analysis of the film was used to distinguish vapor from formic acid/water solutions at differentconcentrations and with a detection limit of 0.01% v/v. The selectivity of the sensor was also investigated. After fumigation with ethanol and other common solvents, there was no response similar to thatfor formic acid. It is believed that films based on lanthanide complexes and chitosan could prevent corrosionand injury from formic acid.

Effect of Glucose and Formic Acid on the Quality of Napiergrass Silage After Treatment With Urea

Yunus, M.,Ohba, N.,Tobisa, M.,Shimojo, M.,Masuda, Y. Asian Australasian Association of Animal Productio 2001 Animal Bioscience Vol.14 No.2

Urea as a silage additive increases crude protein but reduces fermentation quality of silage by increasing pH and enhancing clostridial bacteria growth, especially in low sugar forages. Glucose and formic acid might be expected to compensate these defects caused by urea addition to grass silage. Thus, in this experiment urea formic acid or urea with glucose was applied to improve N content and the quality of napiergrass (Pennisetum purpureum Schumach.) silage. The first growth of napiergrass was harvested at 85 days of age and about 700 g of the grass was ensiled in laboratory silos (1.0 liter polyethylene containers) for 2, 7, 14, and 30 days at room temperature ($28^{\circ}C$). The treatments were no additives (control), urea, urea+glucose or urea+formic acid. Urea was added before ensiling at 0.5% of fresh weight of napiergrass and glucose and formic acid were added at 1% of fresh weight, respectively. After opening the silo, pH, dry matter content (DM), contents on DM basis of total N (TN), volatile basic nitrogen (VBN), lactic acid (LA), acetic acid (AA) and butyric acid (BA) were determined. The control at 30 days of fermentation showed 5.89 for pH with 13.8% for VBN/TN and 1.51% for AA. The addition of urea increased TN by about 1.5% units but decreased the fermentation quality by increasing pH from 5.89 to 6.86, increasing VBN/TN from 13.8% to 24.63%, increasing BA from 0.02% to 0.56%, and decreasing LA from 1.03% to 0.02%. Glucose addition with urea significantly decreased VBN/TN from 13.8% to 4.44% by reducing pH from 6.86 to 4.83 because of higher production of LA (2.62%). Adding urea and formic acid resulted in a more pronounced depression of VBN/TN and fermentation than the addition of urea and glucose. This study suggested that the combination of 1% glucose or 1% formic acid with 0.5% urea will improve nutritive value and fermentation quality of napiergrass silage.