WO2016170492A1 - Traitement d'un composant de charbon - Google Patents

Traitement d'un composant de charbon Download PDF

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Publication number
WO2016170492A1
WO2016170492A1 PCT/IB2016/052265 IB2016052265W WO2016170492A1 WO 2016170492 A1 WO2016170492 A1 WO 2016170492A1 IB 2016052265 W IB2016052265 W IB 2016052265W WO 2016170492 A1 WO2016170492 A1 WO 2016170492A1
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Prior art keywords
coal
bacterial
component
mcc
process according
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PCT/IB2016/052265
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English (en)
Inventor
Ashton Keith COWAN
Gerald Oghenekume EDEKI
Lwazikazi MADIKIZA
Lerato Mary SEKHOHOLA
Michelle Louise ISAACS
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RHODES UNIVERSITY
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RHODES UNIVERSITY
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Publication of WO2016170492A1 publication Critical patent/WO2016170492A1/fr
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Priority to ZA2017/07229A priority Critical patent/ZA201707229B/en
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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C05F11/08—Organic fertilisers containing added bacterial cultures, mycelia or the like

Definitions

  • THIS INVENTION relates to the treatment of a coal component. More particularly, it relates to a biological process for treating a coal component.
  • An object of the present invention is thus to provide means whereby a coal component can effectively be biodegraded and transformed. This is provided by the process of the invention.
  • a bacterial component comprising at least one bacterial strain selected from the group consisting of the following bacterial strains deposited with the Microbial Culture Collection (MCC), Maharashtra, India on 21 October 2013 (KC620476), 4 August 2014 (KC700328 and KC620473), 20 October 2015 (KC620474, KC620478, KC620475), 25 February 2015 (KC758162, KC700329, and KC620477) and 8 April 2015 (KC700330) under the accession numbers as given in Table A:
  • the product i.e. the particulate material
  • the bacterial component may comprise a consortium of two or more of the bacterial strains listed in Table A above.
  • the bacterial component or inoculum may comprise a consortium of different bacterial strains selected from Table A.
  • the bacterial strains may be enriched with a coal medium, e.g. a waste coal medium. More particularly, the bacterial strains may be as specified in Table B. They may be sourced from diesel contaminated soil or a coal slurry:
  • consortium may comprise one of the following combinations of bacterial strains/specie:
  • the process of the invention is characterized thereby that no acid (e.g. nitric acid) pretreatment of the coal component before inoculation thereof with the bacterial component, is required or effected.
  • no acid e.g. nitric acid
  • the process can thus involve obtaining the bacterial strain(s) from a liquid or solid medium containing a hydrocarbon component or a coal component, and then using the bacterial strain(s) to effect the inoculation of the same, or another, coal component, as hereinbefore described.
  • the bacterial strain(s) are obtained from (i) a solid medium in the form of soil, i.e. soil contaminated with a hydrocarbon component such as diesel and/or (ii) a coal slurry.
  • the process thus then involves using a novel bacterial strain obtained from a hydrocarbon contaminated source or a coal source or, preferably, a consortium of two or more such novel bacterial strains to treat a coal site, thereby to biodegrade the coal component at the coal site.
  • the obtaining of the bacterial strain from the liquid or solid medium containing the hydrocarbon or coal component may include isolating the bacterial strain from the liquid or solid medium.
  • the bacterial strain may be isolated from a solid medium in the form of soil contaminated with the hydrocarbon component and/or a coal slurry.
  • the working up of the bacterial strain to produce the bacterial component may comprise combining or formulating at least two bacterial strains obtained as hereinbefore described, into a consortium, with the bacterial component thus comprising a consortium of two or more of the bacterial strains.
  • the bacterial strains may be as listed or specified hereinbefore in Tables A and B.
  • the bacterial component may, in particular, comprise a consortium of two or more of the bacterial strains listed in Table A.
  • the coal component may be as hereinbefore described.
  • the bacterial component may include a minimal mineral salts medium in combination with the bacterial strain or the consortium of bacterial strains.
  • the minimal mineral salts medium may comprise one or more of K 2 HPO 4 , KH 2 PO 4 , NHCI 4 , MgCI 2 and CaCI 2 , and may be an aqueous medium.
  • the aqueous minimal mineral salts medium may then typically comprise (K 2 HPO 4 1 .71 g, KH 2 PO 4 1 .32g, NHCI 4 1 .26g, MgCI 2 6H 2 O 0.01 1 g, CaCI 2 0.02g)/L.
  • the minimal mineral salts medium may be enriched with a trace mineral solution comprising one or more of Na 3 C6H 5 O7, MnSO 4 , CoSO 4 , CoCI 2 , ZnSO 4 , CuSO 4 , AIK(SO 4 ) 2 , H 3 BO 4 , Na 2 MoO 4 , NiCI 2 , Na 2 SeO 3 , V 3+ CI, and Na 2 WO 4 .
  • the trace mineral solution may then comprise (Na 3 C6H 5 O 7 -2H 2 O 2.1 g, MnSO 4 -2H 2 O 0.5g, CoSO 4 or CoCI 2 -6H 2 O 0.1 g, ZnSO 4 -7H 2 O 0.1 g, CuSO 4 -5H 2 O 0.01 g, AIK(SO 4 ) 2 0.01 g, H 3 BO 4 0.01 g, Na 2 MoO 4 -2H 2 O 0.1 g, NiCI 2 -6H 2 O 0.025g, Na 2 SeO 3 0.2g, V(III)CI 0.01 g, Na 2 WO 4 -2H 2 O 0.0033g)/100ml.
  • the process may include adjusting the pH of the enriched minimal mineral salts medium to about 7, e.g. using an acid or base, as required..
  • the bacterial component may be in the form of a liquid suspension.
  • concentration of the bacterial consortium in the suspension may be in the range of 3.42-4.0 x 10 9 cfu/ml, typically 3.62 x 10 9 cfu/ml.
  • the liquid suspension may be applied to the coal component at a rate of 400-500 L/Ha surface area of the coal component.
  • the bacterial component may be in solid form, and may be attached to or form part of inert carrier granules/pellets such as clay-based granules or pellets.
  • concentration of the bacterial consortium in these granules or pellets may be about 1 .5 mg/kg.
  • the granules may be applied to the coal component at a rate of about 200-300 kg/Ha, preferably 250 kg/Ha surface area of the coal component.
  • the coal component may comprise a coal-containing surface layer.
  • the coal component when inoculated with the bacterial component, may be in combination with an inert particulate material.
  • the inert particulate material may be soil, which is thus present in the surface layer together with coal or a coal derivative.
  • the coal-containing surface layer may comprise weathered coal, discard coal, roof coal or any other coal spoils.
  • the process may include adding a neutralizing agent e.g. lime to the coal- containing surface layer, for pH control.
  • a neutralizing agent e.g. lime
  • the process may include harvesting the particulate material, once sufficient degradation of the coal component has taken place.
  • the particulate soil-like material contains organic acids such as fulvic acid and/or organic matter that can readily be transformed into such organic acids such as humic, and the process may include processing the humic particulate material and recovering the organic acids and/or the organic matter.
  • FIGURE 1 shows, for Example 1 , colour change of waste coal containing medium in the presence of bacterial consortia (top panel) and light micrographs indicating attachment of bacteria to coal particles (lower panel);
  • FIGURE 2 shows, for Example 1 , FT-IR spectra of the freeze dried soluble fraction remaining after treatment of waste coal without (A) and with EBRU Culture 10 (B) or EBRU Culture 13 (C) bacterial consortia for 21 days;
  • FIGURE 3 shows, for Example 1 , FT-IR spectra of the freeze-dried insoluble fraction remaining after treatment of waste coal without (A) and with EBRU Culture 10 (B) or EBRU Culture 13 (C) bacterial consortia for 21 days;
  • FIGURE 4 shows, for Example 1 , the decline over time in mass (in grams) of substrate waste coal following exposure to selected bacterial consortia;
  • FIGURE 5 shows, for Example 1 , the decline over time in pH of waste coal media inoculated with selected bacterial consortia
  • FIGURE 6 shows, for Example 1 , the kinetics of production of a humic- like substance from waste coal substrate by the action of selected bacterial consortia;
  • FIGURE 7 shows, for Example 1 , the kinetics of production of fulvic acid from humic acid by the action of selected bacterial consortia
  • FIGURE 8 shows, for Example 3, growth and biomass accumulation by individual strains of the consortium ECCN 42b on discard coal;
  • FIGURE 9 shows, for Example 3, the decline in mass of substrate coal discard by individual strains and the consortium ECCN 42b comprising these strains;
  • FIGURE 1 1 shows, for Example 3, by FT-IR the shift in and formation of new functional groups in residual coal discard material as a result of bacterial and bacterial consortia action for ECCN 42b.
  • Bacteria were isolated from diesel contaminated soil in the Eastern Cape province and from coal slurry in the Mpumalanga province of South Africa. Pure colonies were isolated from bio prospected samples by inoculating coal slurry and diesel contaminated soils in nutrient broth followed by incubation for 48 h at 30 °C after which aliquots were inoculated onto nutrient agar and incubated for a further 24 h. Isolation of pure colonies was carried out after visible growth of the organisms. Ten bacterial strains were isolated and pure cultures of each, enriched with waste coal medium, were put in storage in 80% glycerol medium at -20 Q C.
  • Low grade waste coal also known as, and hence also herein referred to as, discard coal
  • waste coal material obtained from a waste coal dump in Mpumalanga province, South Africa was oven dried at 50°C for 48 h and pulverized to a particle size of 0.2-0.5 mm in diameter. Sterilization of pulverized waste coal material was carried out by freeze-thawing (3 cycles) using liquid nitrogen.
  • Mineral salt medium (MSM, containing K 2 HPO 4 1 .71 g/L, KH 2 PO 4 1 .32 g/L, NHCI 4 1 .26 g/L, MgCI 2 6H 2 O 0.01 1 g/L, CaCI 2 0.02 g /L) which was enriched with 4ml trace mineral solution (TMS containing Na3C6H 5 O7-2H 2 O 2.1 g, MnSO 4 -2H 2 O 0.5g, CoSO 4 or CoCI 2 -6H 2 O 0.1 g, ZnSO 4 -7H 2 O 0.1 g, CuSO 4 -5H 2 O 0.01 g, AIK(SO 4 ) 2 0.01 g, H 3 BO 4 0.01 g, Na 2 MoO 4 -2H 2 O 0.1 g, NiCI 2 -6H 2 O 0.025g, Na 2 SeO 3 0.2g, V(III)CI 0.01 g, Na 2 WO 4 -2H 2 O 0.0033g)/100m
  • Each consortium was coded as EBRU Culture 1 , 2, 3, 4 to 17 and 1 ml of each consortium, in suspension, inoculated into MSM containing waste coal as the only carbon source.
  • a set of un-inoculated samples served as negative controls.
  • positive controls were made up of a consortium of the known strains Pseudomonas aeroginosa, Pseudomonas putida and Bacillus subtilis. All experiments were continuous and carried out at 30 °C for 21 days. Samples were abstracted on days 0, 2, 4, 7, 14, 19 and 21 for analysis of coal solubilization, FT-IR spectroscopy, pH, and determination of mass of residual coal. Each experiment was set up using a complete random block design and replicated three times. Analytical methods
  • FT-IR Fourier transform infrared spectroscopy
  • humic and fulvic acids from waste coal substrate was monitored by extracting using the well documented alkaline extraction method (Igbinigie et at, 2008; Novak et al., 2001 ; Velthorst et al., 1999). Typical solubility parameter curves were obtained when the soluble fraction was separated and the absorbance determined for both humic and fulvic acids at 450 and 370 nm respectively. pH analysis
  • Residual substrate of coal remaining after microbial action was purified by carefully centrifuging at 4000 x g for 20 min. Coal pellets were rinsed with sterile milliQ water and re-centrifuged at 1000 x g for 10 min. Resultant coal pellets were freeze dried and the mass of the dried coal recorded. This method was adopted for all experiments and at the conclusion of each experiment percentage decrease in weight of coal was calculated.
  • Table 1 presents the accession number of each strain, the identity of the organism, and the source. Table 1. Identification of isolated bacteria and Genbank accession numbers
  • Table 2 shows the different bacterial consortia formulated and the codes assigned to each consortium.
  • ECCN is derived from EBRU Culture Collection Number, and 'b' indicates that the culture is in bacterial form.
  • a colour change of the medium was typically observed.
  • EBRU Culture 2 and EBRU Culture 13 rendered the coal enriched medium nearly colourless within 14 d (see Figure 1 top panel).
  • microscopic analysis at ⁇ 40 magnification revealed the close association of these microorganisms with the waste coal substrate particles indicative of attachment (see Figure 1 lower panel).
  • Figure 2 shows the shift in and formation of new functional groups in the soluble fraction of residual waste coal material as a result of bacterial consortia action.
  • Decarboxylation which is the enzymatic and/or chemical removal of carboxyl groups and the release of carbon dioxide from the system had clearly occurred.
  • Figure 3 shows that hydroxylation and methylation were the major reactions that had occurred in the insoluble fraction of residual waste coal material as a result of bacterial consortia action. A total disappearance of ethers, esters, carboxylic acids and anhydrides was observed for waste coal treated with bacterial consortium EBRU Culture 10 (see Fig 3 B, region of 1400- 1200cm "1 ).
  • Figure 4 shows the decline in mass of substrate waste coal over time due to the action of selected bacterial consortia. Greatest loss in mass of substrate waste coal was achieved with EBRU Culture 10 and EBRU Culture 13 and the bulk of the loss in weight occurred between days 7 and 14.
  • Figure 5 illustrates the decline in pH over time of a waste coal containing medium inoculated with selected bacterial consortia. Acidification is the buildup of hydrogen ions, also called protons, reducing the medium pH which occurs when a proton donor is added to the medium. The production of small organic acids and/or proton donors to the medium occurred by bacterial action on waste coal substrate as illustrated by FT-IR analysis of both the soluble and insoluble fractions remaining after inoculation and incubation (see Figures 2 and 3).
  • Humic-like substance is regarded as a major product of the biological breakdown of low ranked coals such as lignite (Sekhohola et al., 2013).
  • Figure 6 shows the kinetics of accumulation of humic-like substance in the soluble fraction of waste coal containing medium inoculated with selected bacterial consortia.
  • Figure 7 shows the kinetics of accumulation of fulvic acid in the soluble fraction of a humic acid containing medium inoculated with selected bacterial consortia.
  • Humic acid which is found in low grade coals such as lignite (Janos, 2003; del Rio et al., 1994: Lobartini et al., 1992), is the organic fraction which is soluble in alkaline media (i.e in 0.1 M NaOH/100ml) and insoluble in acidic media (at pH 1 -2) with average molecular weight of 2,000 to 3,000 Da (Zeng et al., 2002).
  • HA was precipitated from liquid extracts in flasks by adjusting the pH of liquid extracts to ⁇ 1 with 32% HCL. Flasks were left on a rotary shaker for 24hrs at ambient temperature which were later centrifuged at 4000 x g for 90min at 10 °C.
  • Pellets were separated from supernatants with the resultant pellets taken as the humic acid fraction. 0.1 M NaOH was added to supernatants and allowed to stand for 1 hr before they were centrifuged at 4000 x g for 90min. Pellets were separated from supernatants and the supernatants were taken as the fulvic acid fraction.
  • an overnight bacterial consortium i.e. one of the bacterial strains/consortia listed in Tables 2, 3 and 4
  • a medium made of simple sugars such as glucose.
  • Cell biomass is harvested and pelletized in combination with nutrients which may be in the form of fertilizers containing nitrogen and phosphorus.
  • Crushing of heavy coal particles and disking of the upper layer of the coal profile may be carried out for easy access of the bacteria and for oxidation process to take place.
  • Neutralizing agents such as lime for pH control may be added to the coal layer i.e. to the upper 200mm of the coal containing layer.
  • Neutralizing agents may be added at a rate of 20 tons/Ha to 40 tons/Ha, preferably 30 tons/Ha.
  • Inoculation of pelletized bacteria in consortium at a rate of 200 kg/Ha to 300 kg/Ha, preferably 250 kg/Ha may be carried out on the disked coal profile within 100 cm to 200 cm deep, preferably 150 cm deep.
  • Constant irrigation of the coal body may be carried out for speedy oxidation process.
  • extraction of humic acids may be carried out on the oxidized coal.
  • the coal extracted humic acid may be used as a soil conditioner to enhance the growth of plants.
  • one of the bacterial strains/consortia listed in Tables 2, 3 and 4 may be inoculated into a liquid medium containing coal in a batch reactor. Incubation time may be in the range of 30-40 days, preferably, 35 days.
  • the coal medium containing bacteria consortium and minerals may be applied to a body of coal layer which has already been disked and neutralised by liming. Irrigation of the coal layer may be required to facilitate the speedy conversion/breakdown of coal to value added products such as humic-like substances.
  • the coal containing medium is used as an inoculum in treating waste coal dumps, it may also be applied in soils low in humus to act as an organic fertilizer for plant growth enhancement due to the high levels of humic-like substances contained in it.
  • the Applicant has surprisingly found that by means of the process of the invention, a pretreatment step in which the coal component is treated with an acid, such as nitric acid, is not required in order to obtain satisfactory biological remediation of the coal component; furthermore, it has not hitherto been known to use any of the bacterial strains listed in Tables A and B, or any of the consortia listed in Tables 2, 3 and 4, to degrade a coal component. It was also surprisingly found that coal degradation could be effected by bioprospecting organisms, particularly the bacterial strains of Tables A and B or the strains/consortia listed in Tables 2, 3 and 4, from a waste or discard coal site and forming consortia using organisms that degrade both coal and hydrocarbons. Also, it was found that at least some coal degradation can already be observed as soon as 3 days after inoculation of the coal component with the organism or consortia, as evidenced from loss of coal structure and associated colour change (due to depolymerization). References

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

La présente invention concerne un processus biologique de traitement d'un composant de charbon comprenant l'inoculation du composant de charbon 5 avec un composant bactérien comprenant au moins une souche bactérienne choisie dans le groupe constitué des souches bactériennes suivantes déposées auprès de la collection de souches microbiennes (MCC), Maharashtra, Inde, le 21 octobre 2013 (KC620476), le 4 août 2014 (KC700328 et KC620473), le 20 octobre 2015 (KC620474, KC620478, KC620475), le 25 février 2015 10 (KC758162, KC700329 et KC620477) et le 8 avril 2015 (KC700330). On laisse le composant de charbon se biodégrader et se transformer en un matériau particulaire. La souche bactérienne facilite ainsi la biodégradation et la transformation du composant de charbon.
PCT/IB2016/052265 2015-04-22 2016-04-21 Traitement d'un composant de charbon Ceased WO2016170492A1 (fr)

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ZA2017/07229A ZA201707229B (en) 2015-04-22 2017-10-24 Treatment of a coal component

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ZA2015/02749 2015-04-22

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Cited By (2)

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EP4083188A1 (fr) * 2021-04-06 2022-11-02 Geofert LLC Biopréparation bactérienne, son procédé de production et utilisation
CN115430694A (zh) * 2022-08-05 2022-12-06 河南理工大学 一种真菌细菌联合降解低阶煤的方法及其降解率检测方法和降解液环境安全性评价方法

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CN115430694A (zh) * 2022-08-05 2022-12-06 河南理工大学 一种真菌细菌联合降解低阶煤的方法及其降解率检测方法和降解液环境安全性评价方法
CN115430694B (zh) * 2022-08-05 2024-12-13 河南理工大学 一种真菌细菌联合降解低阶煤的方法及其降解率检测方法和降解液环境安全性评价方法

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