WO2015133977A1 - Composition that provides improvement of coal quality and increase in combustion yield - Google Patents

Composition that provides improvement of coal quality and increase in combustion yield Download PDF

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Publication number
WO2015133977A1
WO2015133977A1 PCT/TR2015/000075 TR2015000075W WO2015133977A1 WO 2015133977 A1 WO2015133977 A1 WO 2015133977A1 TR 2015000075 W TR2015000075 W TR 2015000075W WO 2015133977 A1 WO2015133977 A1 WO 2015133977A1
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WIPO (PCT)
Prior art keywords
bacteria
coal
composition according
combination
enzymes
Prior art date
Application number
PCT/TR2015/000075
Other languages
French (fr)
Inventor
Vehbi KOC
Original Assignee
Scs Yenilikci Enerji Teknolojileri Limited Sirketi
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Publication of WO2015133977A1 publication Critical patent/WO2015133977A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/26—After-treatment of the shaped fuels, e.g. briquettes
    • C10L5/32—Coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/02—Microbial additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/18—Spraying or sprinkling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/20—Coating of a fuel as a whole or of a fuel component
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof

Definitions

  • the coal has a sub thermal value of 2.150kcal, the humidity content is 26,45%, the ash rate in original base is 34,5%, total sulphur content is 2,85%.
  • the pyritic sulphur percentage which was 1,51% in the beginning was decreased to 1,11 percent and the slag index was decreased from 0,88 to 0,54; and 25% decrease was realized in the energy that was consumed during the grinding process. 8 to 60% decrease in the emissions (CO,C02,NOx;S02) of coal has been observed in coal combusted in burners and increase up to 100°C has been observed in bed temperatures.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

The invention is related to the fermentation of bacteria and/or production of a combination of oxydase enzymes with white rot fungi in order to be added to iron oxide bacteria that are used to decrease the pyritic sulphur amount and to increase the yield in combustion, to ensure improvement in emissions and to decrease organic sulphur.

Description

DESCRIPTION
COMPOSITION THAT PROVIDES IMPROVEMENT OF COAL QUALITY AND INCREASE IN COMBUSTION YIELD
Technical Field
The invention is related to the biotechnology field, wherein the obtained product is related to a composition which decreases emission and increases burning yield of anthracite comprising carbon, hard coal, bituminous, semi bituminous, lignite, asphaltite and peat coal.
Background of the invention (Prior Art)
Coal is one of the cheaper energy sources and it is one of the main reasons of air pollution in the world. As it is known, coal consists of carbon, hydrogen, oxygen, nitrogen, sulphur, ash, other various elements and humidity. Sulphur inside the coal can be found in three main forms such as organic, pyritic and sulphate forms. The sulphur found inside the coal is released into the atmosphere as S02 during the burning of the coal; and at the same time NOx's are formed due to the usage of excessive combustion air and thermal procedures and this also needs to acid rains. The pyritic sulphur found inside coal, is assumed to be one of the main reasons for the formation of slag inside a burner during combustion; organic and pyritic sulphur together lead to erosion inside the burner.
Several methods have been used in order to overcome the disadvantages mentioned in the previous paragraph, and one of these methods is to utilize bacteria or enzymes. According to a preliminary research carried out, a study wherein bacteria and enzymes are used together as a combination has not been found.
In an article published by Southern California University [Lee, K., & Lee, K. (n.d.). Coal Desulfurization Through Reverse Micelle Biocatalysis Process. (Southern California)], it has been mentioned that Sulfolobus acidocaldarius' which is a thermophilic bacteria or an enzyme extract of Thiobacillus ferrooxidans could be used for coal de-sulphurization; however an idea regarding the combination of enzymes and bacteria was not mentioned. Moreover the process (reversible micelle biocatalysis process) within the article, and the aim, technique and contents are significantly different from the present invention. An enzyme composition and method is described in the patent numbered US 2010/0151554, which is used to decrease the NOx and SOx emissions, comprising laccase, pyruvate dehydrogenase, de-hydrolipoii transacetylase and dehydrolipoil dehydrogenase and a coenzyme. Although the contents and the process are also different from the present invention again a combination of bacteria and enzymes have not been mentioned.
According to the patent numbered KR 100390973 an enzymatic supplement which is added in order to increase the combustion yield of the coal and petrol is being described and a bacteria and enzyme combination has not been mentioned in this document either.
Brief description of the invention and its aims
The invention is related to the fermentation of bacteria by adding iron oxidizing bacteria in order to decrease the pyritic and organic sulphur and/or to the production of oxidase enzyme combinations by adding white rot fungi that used in order to decrease emissions and increase combustion yield.
The aim of the invention is to prevent the wastage of sources by using coal more efficiently, and to decrease the environmental pollution down to more acceptable levels by means of decreasing the S02, NOx, CO, C02 pollutants that are being released into the atmosphere. The invention is related to a composition which provides improvement in all industrial and domestic domains that provide thermal energy via the combustion of coal such as electricity producing power plants, cement factories and the iron-steel sector, and said composition aims to decrease slag, pyritic sulphur and pollution, to improve millable index, to decrease ash and to increase the combustion yield.
Brief description of the drawings
Figure 1: S02 emission graphic
Figure 2: C02 emission graphic
Figure 3: CO emission graphic
Figure 4: NOx emission graphic
Figure 5: Excess air rate graphic Detailed description of the invention
The decreasing of pyritic sulphur, slag and pollution which are the aims of the invention is carried out by using iron oxidizing bacteria. Rusticyanin and/or Acidithiobacillus bacteria is being used as iron oxidizing bacteria. The invention is related to the fermentation of bacteria and/or production of a combination of oxydase enzymes with white rot fungi in order to be added to iron oxide bacteria that are used to decrease the pyritic sulphur amount and to increase the yield in combustion, to ensure improvement in emissions and to decrease organic sulphur; wherein the enzymes that are produced are catechol oxidase, O-di'pheno) and/or laccase, P-diphenol and/or cresolase or monophenol mono oxygenase and/or Ligninperoxidase and/or Mangan-peroxidase and/or oxidase independent from Manganese and/or acidic Manganese Peroxidase and/or tyrosinase.
The enzyme combination and the bacteria combination is mixed when the pH is between 2- 10, preferably 3-6, and in order for this new combination that has been formed to be applied homogenously to the surface of the coal it is diluted with water, and following this the target is reached when the application is carried out after dilution and after the coal is kept for 4 to 30 days under atmospheric conditions.
The composition is formed of catechol oxidase, O-diphenol and/or laccase, P-diphenol and/or cresolase or monophenol mono oxygenase and/or Ligninperoxidase and/or Mangan- peroxidase and/or oxidase independent from Manganese and/or acidic Manganese Peroxidase and/or olive black water for the production of tyrosinase within the group of oxidase enzymes, melas obtained from the wastage of sugar factories, schlempe, sugar cane pulp, agricultural wastage, fruit juices, paper, beer, factory wastage producing wine etc, and carbon and phenol derivatives (mono, di and polyphenol), lignin, cellulose, substrates comprising one or more of wood like products comprising hemi ceiiuiose, and together with this white rot fungi obtained by isolating thereof from soil, sediments and composts continuously or with intervals and bacteria such as Cversicolor, F.trogii, P.sajor, Aspergillus, Geotrichum, Phanerochaete, Trametes vescolor, Trichosporon cutaneum, Candida tropicalis, Geotrichhum, Penicillum, Bacilus, Azosiprillum, martnomonas, Streptomycetes, Rhodotorula giutinis, Debaryomyces hansenii etc, copper manganese and iron additions that have been fermented with yeast or as cofactors.
Bacteria that oxidize iron used for pyritic sulphur, is obtained through
Acidithiobacillus bacteria isolated from river beds that are present in coal, iron and mine regions, and is produced and used via the production of Rusticyanin by extracting as a result of binding protein to copper which was obtained from the forms containing iron and non iron forms of ThiobaciHus ferrooxidans and/or ThiobaciHus thiooxidans.
The enzyme and bacteria combinations that are separately produced are adjusted according to their pyritic sulphur and organic sulphur rates found inside the coal and then are mixed. The final product preferably comprises iron oxidizing bacteria up to the amount of lOxlO6 cfu/ml in accordance with the amount of pyritic sulphur and iron rate within the coal, and enzyme up to the amount of 1 x ICJ3 ppm to 1 x 103 ppm adjusted according to the ash, humidity and organic sulphur rate within coal.
The solution that has been obtained by diluting the bacteria and enzyme combinations is applied to the surface of the coal by homogenously mixing said solution between the ranges of %1 to 10% by weight of the coal.
The product that has been produced can be applied to coal within pulverized coal technology, fluidized bed, nucleate fluidized bed, super critical fluidized bed, circulating fluidized bed, coal fed steamboiier and can be applied to heating in homes under the conditions mentioned above.
Following the tests that have been carried out, up to 50% decrease in NOx amounts that have been released into the atmosphere following application, 1/9 decrease in comparison to similar methods in CO amount, 8% decrease in C02 amount, up to 60% decrease in SO* amount, 30% decrease in slag amount, up to 35% decrease in pyritic sulphur rate and 25% decrease in the grindability index was observed.
EXAMPLE 1
Rusticyanin which is extracted depending on copper, and enzyme group (diluted inside water together with the buffer solution of peroxidase, trvosinase, laccase, oxyreductase, between 0,001 to 1% surfactant dilutes inside water and 20 to 80 qlvserine) produced according to the fermentation from olive black water has been mixed together and has been applied as 4% by weight of the coal to the coal having a particle size between 0 to 50mm. The coal has been kept for 10 days under atmospheric conditions, following this has been grounded between 0 to 10mm in order to be combusted and has been fed into the 550mw thermal capacity steamboiier. The coal has a sub thermal value of 2.150kcal, the humidity content is 26,45%, the ash rate in original base is 34,5%, total sulphur content is 2,85%. The pyritic sulphur percentage which was 1,51% in the beginning was decreased to 1,11 percent and the slag index was decreased from 0,88 to 0,54; and 25% decrease was realized in the energy that was consumed during the grinding process. 8 to 60% decrease in the emissions (CO,C02,NOx;S02) of coal has been observed in coal combusted in burners and increase up to 100°C has been observed in bed temperatures.
The test data obtained as a result of the application of sample production to coal are between 1 to 10 reinforced coal data, whereas 11 to 16 data are the data of non reinforced coal fed to the burner (in both types of coal 10% limestone CaO is present)

Claims

1. Coal coating composition characterized in that; the bacteria and enzymes comprise multiple combinations.
2. Composition according to claim 1, characterized in that the bacteria are Rusticyanin and/or Acidithiobacillus.
3. Composition according to claim 1, characterized in that the enzymes are oxidase enzymes that have been obtained by fermentation of bacteria or white rot fungi.
4. A composition according to claim 3, characterized in that the enzyme is chosen from a group comprising catechol oxidase, O-diphenol and/or laccase, P-diphenol and/or cresolase or monophenol mono oxygenase and/or Ligninperoxidase and/or Mangan-peroxidase and/or oxidase independent from Manganese and/or acidic Manganese Peroxidase and/or olive black water for the production of tyrosinase or a combination thereof.
5. A composition according to claim 2, characterized in that it comprises Rusticyanin extracted from protein that binds to copper obtained from the river beds located in the region of iron oxidizing bacteria, or from Acidithiobacillus bacteria isolated from coal, iron and ore mines, or from the forms comprising iron or non iron forms of Thiobacillus ferrooxidans and/ 'or Thiobacillus thiooxidans.
6. A composition according to claim 3, characterized in that it comprises enzymes obtained from olive black water melas obtained from the wastage of sugar factories, schlempe, sugar cane pulp, agricultural wastage, fruit juices, paper, beer, factory wastage producing wine etc, and carbon and phenol derivatives, lignin, cellulose, substrates comprising one or more of wood like products comprising hemi cellulose, and together with this white rot fungi obtained by isolating thereof from soil, sediments and composts continuously or with intervals and bacteria such as C.versicolor, F.trogii, P.sajor, Aspergillus, Geotrichum, Phanerochaete, Trametes vescolor, Trichosporon cutaneum, Candida tropicaiis, Geotrichhum, Penicillum, Bacilus, Azosiprillum, marinomonas, Streptomycetes, Rhodotorula glutinis, Debaryomyces hansenii etc, fermentation with yeasts, copper as cofactor, manganese and iron additions.
7. Composition according to claim 1, characterized in that it comprises enzymes obtained from olive black water.
8. Composition according to claim 1, characterized in that it comprises up to 10 x 106 cfu/ml iron oxidizing bacteria or bacteria combination.
9. Composition according to claim 1, characterized in that it comprises between 1 x 103 to Ix 103 enzymes or enzyme combination.
10. Usage of the composition according to claim 1, characterized in that it comprises; a. Mixing of the separately produced enzyme combination and bacteria combination between pH 2-10 ranges, preferably between the ranges of 3-6,
b. Dilution of the new combination as 1% to 10 % by weight of the coal with water in order to be able to homogenously apply said combination onto the surface of the coal, c. Applying the combination mentioned in article (b) to the coal,
d. Leaving the treated coa! under atmospheric conditions for 4 to 30 days.
PCT/TR2015/000075 2014-03-06 2015-02-26 Composition that provides improvement of coal quality and increase in combustion yield WO2015133977A1 (en)

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TR2014/02691 2014-03-06

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106701245A (en) * 2017-02-22 2017-05-24 董地 Straw biomass combustion rod applicable to new energies and preparation method thereof
WO2017095895A1 (en) * 2015-12-02 2017-06-08 Nox Ii, Ltd. Enzyme treatment of coal for mercury remediation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100390973B1 (en) 2002-02-06 2003-07-12 Millae Tech Co Ltd Enzyme-based fuel additive
US20100151554A1 (en) 2008-12-15 2010-06-17 Ein Int'l Co. Ltd. Enzyme composition and use therefore

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100390973B1 (en) 2002-02-06 2003-07-12 Millae Tech Co Ltd Enzyme-based fuel additive
US20100151554A1 (en) 2008-12-15 2010-06-17 Ein Int'l Co. Ltd. Enzyme composition and use therefore

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AYTAR P ET AL: "Desulphurization of some low-rank Turkish lignites with crude laccase produced from Trametes versicolor ATCC 200801", FUEL PROCESSING TECHNOLOGY, ELSEVIER BV, NL, vol. 92, no. 1, 1 January 2011 (2011-01-01), pages 71 - 76, XP027429856, ISSN: 0378-3820, [retrieved on 20100925], DOI: 10.1016/J.FUPROC.2010.08.022 *
KWANG-IL LEE ET AL: "Coal desulfurization through reverse micelle biocatalysis process", PREPR. PAP., AM. CHEM. SOC., DIV. FUEL CHEM, BIOPROCESSING OF COAL, 1 January 1988 (1988-01-01), 1988, pages 573 - 579, XP055191487 *
KWANG-IL LEE ET AL: "SULFUR REMOVAL FROM COAL THROUGH MULTIPHASE MEDIA CONTAINING BIOCATALYSTS", JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY, JOHN WILEY & SONS LTD, UNITED KINGDOM, vol. 48, no. 1, 1 January 1990 (1990-01-01), pages 71 - 79, XP000104150, ISSN: 0268-2575 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017095895A1 (en) * 2015-12-02 2017-06-08 Nox Ii, Ltd. Enzyme treatment of coal for mercury remediation
CN108602014A (en) * 2015-12-02 2018-09-28 Nox Ii 国际有限公司 The enzymatic treatment of coal for mercury reparation
US10760026B2 (en) * 2015-12-02 2020-09-01 Nox Ii, Ltd. Enzyme treatment of coal for mercury remediation
CN106701245A (en) * 2017-02-22 2017-05-24 董地 Straw biomass combustion rod applicable to new energies and preparation method thereof

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