Showing posts with label glycerol. Show all posts
Showing posts with label glycerol. Show all posts

Thursday, February 12, 2009

Purification of Crude Glycerol for Omega-3 Fatty Acids Production

According to Biodiesel Magazine, a technology was developed by Wen at Virginia Tech that uses glycerin to aid in the production of algae that produce omega-3 fatty acids. For this purpose,the soap and methanol present in crude glycerin must be removed before it can be used to aid in the algae growth.

When adjusting pH of the medium containing crude glycerol for algae to grow, the soap contained in the glycerol will be precipitated out of the medium, i.e. the process used to adjust the pH of the solution causes the soap to solidify and settle out of the glycerin.

Next when the glycerin is sterilized at 120 C before used to cultivate algae, the residual methanol will be evaporated and collected.

Sunday, January 4, 2009

Oxidation of Glycerol

Glycerol can be oxidized to produce fine and specialty chemicals. Traditionally, oxidation can be conducted by mineral acids, enzymatic, or electron-chemical processes but selective catalytic oxidation turns to be productive, cheaper, and environmental friendly.

Oxidation products are useful as intermediates. e.g. glyceric acid is an intermediate for medicine manufacture; dihydroxyactone is a self-tanning agent in cosmostics; tartronic acid is an chelating agent; hydroxypyruvic acid is used for fruit maturation and intermediate for amino acids;Mesoxalic acid has potential application in organic syntheses.

Most of recent studies focus on heterogeneous catalysts such as supported platinum or palladium, and gold etc while some on homogeneous catalyst such as TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl).

The oxidation ususlly use air or oxygen as an oxidant at mild temperature (20-80 C) in the liquid pahse. The pH has an important impact on catalyst performance, product coversion rate and selectivity.

Saturday, January 3, 2009

Purification of Crude Glycerol

The glycerol obtained from transesterification is separated from biodiesel by gravity. The concentration of this type of glycerol is ~50% (wt),which is so-called raw glycerol and contains the contaminants such as alcohol, soap, base catalyst, salts, and untreated organic materials.

Crude glycerol can be obtained through the following purification of raw glycerol:

  1. Acidification of the soaps with HCl and separation of formed free acids by gravity
  2. Neutralization with caustic soda
  3. Evaporation for methanol recovery and water removal. The methanol recovered can be reused for biodiesel production. The the crude glycerol with 80-85% (wt.) can be obtained.

Crude glycerol purification:

  1. Crude glycerol can be purified by vacuum distillation to a purity of 99.5% (wt).
  2. Crude glycerol with diluted salt can be refined with ion-exchange
  3. Crude glycerol with high salt content can be purified with ion exchange chromatography and thin film distillation.

Tuesday, December 30, 2008

Conversion of Glycerol to 1,3-Propanediol

Microbial Conversion of Glycerol to 1,3-Propanediol: Physiological Comparison of a Natural Producer, Clostridium butyricum VPI 3266, and an Engineered Strain, Clostridium acetobutylicum DG1(pSPD5). Abstract: Clostridium acetobutylicum is not able to grow on glycerol as the sole carbon source since it cannot reoxidize the excess of NADH generated by glycerol catabolism. Nevertheless, when the pSPD5 plasmid, carrying the NADH-consuming 1,3-propanediol pathway from C. butyricum VPI 3266, was introduced into C. acetobutylicum DG1, growth on glycerol was achieved, and 1,3-propanediol was produced. In order to compare the physiological behavior of the recombinant C. acetobutylicum DG1(pSPD5) strain with that of the natural 1,3- propanediol producer C. butyricum VPI 3266, both strains were grown in chemostat cultures with glycerol as the sole carbon source. The same “global behavior” was observed for both strains: 1,3-propanediol was the main fermentation product, and the qH2 flux was very low. However, when looking at key intracellular enzyme evels, significant differences were observed. Firstly, the pathway for glycerol oxidation was different: C. butyricum uses a glycerol dehydrogenase and a dihydroxyacetone kinase, while C. acetobutylicum uses a glycerol kinase and a glycerol-3-phosphate dehydrogenase. Secondly, the electron flow is differentially regulated: (i) in C. butyricum VPI 3266, the in vitro hydrogenase activity is 10-fold lower than that in C. acetobutylicum G1(pSPD5), and (ii) while the ferredoxin-NAD reductase activity is high and the NADH-ferredoxin reductase ctivity is low in C. acetobutylicum DG1(pSPD5), the reverse is observed for C. butyricum VPI 3266. Thirdly, actate dehydrogenase activity is only detected in the C. acetobutylicum DG1(pSPD5) culture, explaining why his microorganism produces lactate.


Production of 1,3-Propanediol from Glycerol by Clostridium cetobutylicum and Other Clostridium Species. Abstract: Glyceol was fermented with the production of 1,3-propanediol as the major fermentation product by four strains of Clostridium acetobutylicum, six of C. butylicum, two of C. beijerinckii, one of C. kainantoi, and three of C. butyricum. 1,3-Propanediol was identified by its retention times in gas chromatography and high-pressure liquid chromatography and by its mass spectrum. During growth of C. butylicum B593 in a chemostat culture at pH 6.5, 61% of the glycerol fermented was converted to 1,3-propanediol. When the pH was decreased to 4.9, growth and 1,3-propanediol production were substantially reduced.


Use of Glycerol from biodiesel production: Conversion to added value products. Abstract: A detailed study of main stages of a novel no-conventional process to obtain 1,3-propanediol (PD) from glycerol (Gly) has been made. Initially the volumetric productivity of Gly fermentation with Klebsiella pneumoniae bacterium was optimized for one and two continuous stages, where was necessary to study the multiplicity of stable steady states for the fermentation system selecting the conditions where higher concentrations of PD are found; and under optimal operation conditions the outlet PD concentration and the global yield are 0.4833 mol/l and 0.5481 molPD/molGly, respectively. For PD recovery from fermentation broth a no-conventional separation scheme was proposed, which consists first in a reactive-extraction with iso-butyraldehyde (iBAld) for produce 2-iso-propyl-1,3-dioxane (iPDOx) and water. The iPDOx is removed toward the organic phase by the aldehyde that acts simultaneously as reagent and solvent. The yield of reactive-extraction process is 85%. Finally Static Analysis (SA) for iPDOx hydrolysis system shows that is possible to obtain PD of high purity and recovery the aldehyde at the 88% in a reactive-distillation tower. SA also allowed obtaining the technological configuration of reactive-distillation tower and this technological synthesis was validated starting from simulations to both infinite/infinite and finite/finite (stages/reflux) conditions, using the ASPEN PLUS® software. For finite conditions the simulations showed that a conversion of 69% and 97.5% is reached for reflux ratios of 5.73 and 9.5 respectively.


HIGH PRODUCTION OF 1,3-PKOPANEDIOL FROM GLYCEROL BY Closhdium butyricum VPI 3266 IN A SIMPLY CONTROLLED FEDBATCH SYSTEM. Abstract: A simple fed-batch system which controls substrate feeding by measuring the CO, produced during the fermentation, was developped. This Fed-batch approach allowed high production of 1,3-propanediol from glycerol by Clostridium butyricum by avoiding substrate inhibition phenomena. 65 g/l of 1,3-propanediol was produced with a productivity of 1.21 g/l.h and a yield of 0.56. The concentration of 1,3-propanediol obtained and the productivity were significantly higher than those reached in batch culture.


CATALYTIC CONVERSION OF GLYCEROL AND SUGAR ALCOHOLS TO VALUE-ADDED PRODUCTS. Ph.D.Thesis.

Sunday, December 28, 2008

Value-added Chemicals from Crude Glycerol

According to a new research paper, bBoth conventional catalysis and biological conversion can offer promising opportunities for the biodiesel industry to convert crude glycerol into a wide variety of value-added products.

A list of compounds that can be made via oxidation or reduction of glycerol are:

  1. Tartronic acid (C3H3O5)
  2. Dihydroxyacetone
  3. Mesoxalic acid (Ketomalonic acid)
  4. Glyceraldehydes
  5. Glyceric acid
  6. Malonic acid
  7. Hydroxypyruvic acid
  8. Lactic acid
  9. Pyruvic acid
  10. Propylene glycol
  11. Propionic acid
  12. Glycidol
  13. Acrylic acid
  14. Propanol
  15. Isopropanol
  16. Acetone
  17. Propylene oxide
  18. Propionaldehyde
  19. Allyl alcohol
  20. Acrolein
  21. Hydrogen


Production of various coproducts via anaerobic fermentation of glycerol by clostridia:

  1. 1,3-PDO
  2. Acetic acid
  3. Butyric acid
  4. Lactic acid
  5. Succinic acid
  6. Butanol
  7. Ethanol
  8. Acetone

Sunday, December 21, 2008

The fate of glycerin from biodiesel production

Glycerin, or glycerine, is a by-product of biodiesel production. Supply of glycerin in the United States and worldwide is projected to grow over the next decade as government policies and incentives favor increased processing of plant oils for production of biodiesel fuels (For every 9 kilograms of biodiesel produced, about 1 kilogram of a crude glycerin by-product is formed; ). Sooner or later, the amount of glycerin produced will exceed the amount consumed by the market today. The prices in the glycerin market will continue to drop and eventually, glycerin will become an environmental liability.

Currently, up to 10% of the dietary dry matter could be supplied by glycerol with no decreases in feed intake or alterations of performance in growing ruminants or lactating cows. However,
there are some concerns with glycerin as a feedstuff due to its contents of methanol and mineral salts such as potassium salts and phosphates.
Today, biodiesel production plants are in need of methods to realize increased income from this glycerol and solve the fate of glycerol as a by-product.
One of the potentioal solutions is to convert the crude natural glycerol to propylene glycol. Some of the benefits of this technology are to utilize the waste and produce propylene glycol from a renewable source raw material. Of course, this technology could be used in biodiesel production plants to increase profitability.