EP2793608A1 - Biopolymers isolated from residual biomass and fossil source; production processes and product use - Google Patents
Biopolymers isolated from residual biomass and fossil source; production processes and product useInfo
- Publication number
- EP2793608A1 EP2793608A1 EP12824749.1A EP12824749A EP2793608A1 EP 2793608 A1 EP2793608 A1 EP 2793608A1 EP 12824749 A EP12824749 A EP 12824749A EP 2793608 A1 EP2793608 A1 EP 2793608A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- biopolymers
- sbp
- organic
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
- A23K10/37—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/20—Shaping or working-up of animal feeding-stuffs by moulding, e.g. making cakes or briquettes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/25—Shaping or working-up of animal feeding-stuffs by extrusion
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/30—Feeding-stuffs specially adapted for particular animals for swines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C05F9/00—Fertilisers from household or town refuse
- C05F9/04—Biological compost
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
- C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
- C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
- C08L89/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Definitions
- the invention concerns the. chemical composition, the production and the uses of water soluble biopolymers isolated form residual biomass and from fossil source.
- biomass treatment technology has been developed mainly to perform combustion for the production of thermal and electrical power, chemical reactions to obtain biodiesel, and fermentation to yield biogas and bioethanol.
- Such technologies are however expensive. They, cost more than the market value of the obtained energy or fuel. The reason for this is due to a number of unfavorable features which are typical of biomass: i.e.
- the invention comprises a mix of water soluble biopolymers (SBP) constituted by two basic parts, one organic and the other mineral. These two parts aire intimately bonded to each other.
- the organic fraction is composed by molecules with molecular weight comprised between 5 and 500 kDalton ' and polydispersivity index between 6 and 53.
- the mineral fraction contains silicon, iron, aluminum, magnesium, calcium, potassium, sodium, copper, nickel, -zinc, chromium, cadmium and lead.
- This water soluble biopolymers' mix is obtained according to a procedure comprising the following steps: a. to provide biomass or fossil material containing organic matter;
- the water soluble biopolymers mix constituting the matter of the present invention, may be used as follows:
- SBP water soluble biopolymers
- the SBP potential monetary value in the chemicals' market may be estimated from 1 to several tens € kg -1 .
- This potential revenue is from 5 to hundred times higher than that obtainable from the same sourcing biowaste upon using it for the production of thermal power by combustion (about 0,20 € kg "1 of organic matter) or as fertilizer by composting (about 0,024 € kg -1 of organic matter) .
- the product and processes of the present invention if adequately integrated within the current waste treatment plants processing urban biowastes o residual biomass from other source, may contribute to turn such waste treatment plants into biorefinery, where the waste treatment cost is compensated form the revenue obtained by the SBP sale.
- biowastes would not be solely an economic burden for society, but become source of revenue and new jobs.
- SBP water soluble biopolymers
- the invention is applied also to any potential fossil source of SBP. It is primarily meant for the valorization of residual biomass produced by human activities in order to be exploited as source of products to use in chemical and environmental technology, in agriculture and animal husbandry, and thus to replace partly or entirely current commercial products used for the same above applications.
- the first form of application of the present invention is the chemical composition of new products of natural biological source, named water soluble biopolymers (SBP) .
- SBP water soluble biopolymers
- These products are entirely new, since the below reported composition has never before described and/or reported by anyone.
- the peculiarity of the chemical composition of SBP lies in the presence of both the organic and mineral components, where the organic fraction is bonded to the mineral fraction, both having a sinergic role. In essence, the organic component keeps in solution the mineral component, and the latter in turn . modulates the properties and behavior of the organic component.
- the SBP organic fraction is described in more details as a mixture of molecules with 5-500 kDalton molecular weight and 6-53 polydispersivity index.
- Such polymeric molecules are characterized by the presence of aliphatic carbon chains, aromatic carbon, and polar functional groups, free and/or bonded to the above reported mineral elements, to yield the following % weight relative chemical composition: 37 ⁇ C ⁇ 65; 3 ⁇ N ⁇ 7; ceneri ⁇ 30; Si ⁇ 3,0; Fe ⁇ 0,9; Al ⁇ 0,8; Mg ⁇ 1,2; Ca ⁇ 6,5; K ⁇ 10; Na ⁇ 10; Cu
- N e C mean organic nitrogen and carbon distributed over the above described carbon types and functional groups with the following composition expressed as mole fraction of the specific carbon type over the product total organic C:.-0,3 ⁇ C al ⁇ 0,6; CN ⁇ 0,1; OMe
- the analytical protocol to identify and characterize the SBP comprises the determination of i) mineral elements by atomic absorption e ii) of C and N by microanalysis, potentiometric titration of COOH e PhOH groups, solid state 13 C nuclear magnetic resonance, and elaboration of experimental data described in the examples' section.
- the second form of application of the present invention lies in the SBP source.
- the SBP are isolated from residual biomass of urban, agriculture, forest, agroindustrial, animal (as for instance manure) and industrial source, such as for example, lignin and polysaccharide material contained in the liquor of the cellulose pulp process, in the wastes of the wood processing industry, of the food industry, of slaughter houses, in sewage sludge.
- the SBP can also be obtained from fossils such as peat, lignite, leonardite.
- the third form of application of the present invention lies in the process to obtain the SBP.
- the SBP can be obtained using two process, separately or combined, hereinafter named hydrolysis/precipitation separation process (SP) and hydrolysis/membrane separation process (MS) .
- SP hydrolysis/precipitation separation process
- MS hydrolysis/membrane separation process
- Each process comprises two phases, hereinafter named hydrolysis and product separation; the two processes differ one from the other in the separation phase.
- the above specified residual biomass (RBM) or fossil material is treated with water at 8-13 pH for 2-4 hours with a liquid/solid ratio comprised between 8 and 4 and at temperature comprised between 60 e 200 °C.
- the settled solid phase containing the insoluble organic residue (IOR) is separated from the surnatant liquid phase containing the soluble organic substances (SOS) produced by the RBM hydrolysis.
- the SOS separation is performed by one or both the SP o MS processes.
- the SOS phase is acidified to pH ⁇ 4 in order to precipitate the SBP products. These are recovered in solid form by centrifugation and/or filtration, followed by washing and drying.
- the SOS phase is pumped through a microfiltration (MF) , ultrafiltration (UF) , nanofiltration (NF) or dialysis membrane unit to yield a retentate (RF) and a permeate (-PF) phase.
- MF microfiltration
- UF ultrafiltration
- NF nanofiltration
- RF retentate
- -PF permeate
- the RF phase contains the SBP in solution or gel form up to 17 % concentration and the desired pH, without need of adding other reagents to correct pH to the desired value.
- the RF may be used as such or after drying to produce solid SBP.
- the PF phase eventually added with alkali to the desired pH, is recycled to the hydrolysis reactor to perform the reaction for the next RBM lot.
- the PF is enriched until saturation with organics having molecular weight below 5000 D.
- the PF phase is dialyzed to yield water to recycle to the hydrolysis reactor and a concentrated solution of organics. This latter, after water evaporation, yields a residue containing organics with molecular weight below 5000 D.
- the SBP products obtained as above have 25 % ash content, due to the presence of the mineral elements.
- the following procedure yields SBP with reduced mineral content. Acidifying the above RF to pH 1,5-3 yields a precipitate. This is separated from the acid mother solution by centrifugation and/or filtration, washed repeatedly with HC1 or HF solution and dried. As shown below, the reduced mineral content changes the properties and performances of the product. The reduced mineral content occurs due to the following reactions:
- M is the mineral element
- HX is the mineral acid
- RCOOM, PhOM e CNDDDM are the carboxylic, phenol and amino groups holding M with ionic and donor-acceptor bonds
- RCOOH, PhOH e CNDDDM are the corresponding metal free organic functional groups.
- a fourth form of putting into practice the present invention is the use of SBP, and the related process, as auxiliaries for remediation of soil and waters contaminated by undesired organics and metals.
- Te process is based on the interaction between SBP in solution and one or more contaminants (C) , either organic and mineral, which are present in the soil or water to be remediated. This interaction yields the SBP-C adduct in solution. The adduct can then be easily separated by precipitation at acid pH o ultrafiltration.
- C contaminants
- the SBP are sequestering agents for the C contaminants. In this fashion, the biopolymers donate to the contaminant their same solubility properties. By bonding .
- the SBP increase the contaminant water solubility at pH > , do not allow the contaminant to permeate through ultrafiltration membranes with molecular cut off above 5000 kDalton, and precipitate together with the contaminant at acid pH.
- SBP-C adduct form Typical examples to use the SBP according to this mechanism are described in the examples reported below. These examples show how, by use of SBP, either the SBP and the contaminant may be recovered in SBP-C adduct form, at 98-99 % level. It is possible in this fashion to perform efficient remediation of the soil or water to be treated, producing solid and liquid effluents meeting the legislation requirements for their use, except for the SBP- C adduct.
- the adduct, separated by precipitation or membrane ultrafiltration, can be disposed by incineration to yield a mineral residue to recycle to the chemical industry for further uses.
- the above process may also be used for the selective recovery of specific heavy metals, for example V, Cu, . n, Cd, Hg, Pb, Ni / Cr, Ag and others, from waste materials such as obtained by treating any refuse by incineration of the organic fraction.
- specific heavy metals for example V, Cu, . n, Cd, Hg, Pb, Ni / Cr, Ag and others.
- the same process may be used for the. abatement of COD industrial organic waste effluents, for example exhausted dyeing baths of the textile industry and others .
- a fifth form of putting into practice the present invention is using SBP to inhibit the mineralization of organic N, or to decrease the ammonia content, in anaerobic fermentation processes of any nature, such as those for production of biogas, or of any biofuel, starting from dedicated crop or from residual biomass of urban, agriculture, and agro-industrial source, and the fermentation processes occurring in the animal digestive tract.
- the addition of SBP in adequate amounts to the fermentation liquor allows to optimize the biogas production process, by enhancing the product yield, and to obtain a digestate with reduced ammonia content by 30 %. or more.
- the mineralization of the organic N results in lower feed utilization for the animal growth, and thus in reduced animal growth rate.
- the N mineralization also increases ammonia and/or nitrogen •oxides emission in the animal dejections, which therefore impact negatively on soil, and on surface and ground waters quality.
- the addition of SBP in adequate amounts to the animal diet allows to decrease the mineralization of organic N, to enhance the animal growth rate and to reduce the environmental impact of animal dej ections .
- the SBP allow to obtain a process effluent, either gaseous, and liquid or solid (the bioreactor digestate or the animal dejections) , with reduced environmental impact, with significant - economic benefits for waste treatment facilities and for the animal production industry.
- a sixth form of putting into practice the present invention is the use of SBO as binding agents.
- the SBP may be used as binder for the fabrication of objects in the desired form, said objects comprising organic or inorganic oxides components.
- the example section describe for instance the fabrication of animal feed in pellet form.
- the binding properties of SBP may be exploited for the manufacture of materials and objects for house building and road construction, such as cement, ceramic tiles, road pavement, or used in any other industrial sector where binders are required.
- a seventh form of putting into practice the present invention is using SBP at proper dose in order to enhance photosynthesis, with consequent increase of plant leaf chlorophyll content, and of plant growth and agriculture productivity.
- SBP SBP at proper dose to soil used for cultivation of horticultural species enhances leaves chlorophyll content, plant growth rate, and early and total fruit production at the end of the cultivation/growth cycle.
- stirring is stopped, and the solid/liquid suspension is allowed to settle until the surnatant liquid phase flows easily through a 0.125 mm sieve. This allows to separate and collect about 70 % of the starting liquid volume.
- the collected liquid phase contains the water soluble organic substances (SOS) , produced by hydrolyzing the starting RBM.
- SOS water soluble organic substances
- the residual liquid phase about 30 % of the starting alkaline water, is retained by the solid phase settled in sludge consistency.
- This material contains the insoluble organic residue (IOR) , and part of SOS contained in the water phase retained by the settled IOR.
- the sludge is washed with a volume of fresh water equal to 30 % of the starting volume of alkaline water before the hydrolysis, in order to displace the SOS phase retained by the IOR solid phase.
- the surnatant liquid phase is withdrawn from the reactor and added to the hydrolyzate first removed from the reactor.
- the total collected liquid contains SOS at 3 % concentration and pH 10.
- This liquid is conveyed to the ultrafiltration membrane having 5 kD cut off.
- the membrane inlet and outlet pressure values are 4 and 2 bar respectively. This allows to obtain a retentate (SOSRUF) volume equal to 25 % of the inlet volume.
- the permeate (SOSPUF) having 11 pH, contains 0,5 %, or less, of water soluble organics with molecular weight below 5 kDalton.
- SOSRUF contains the SBP with molecular weight above 5 kDalton. These products have relative chemical composition within the ranges above specified (see first form of application) .
- the SOSRUF - may be dried to yield SBP in solid form or used as such depending on the product intended successive use.
- the SOSPUF is recycled to the hydrolysis reactor to wash IOR, or to repeat the hydrolytic treatment on the same IOR, or to perform the hydrolysis of a new RBM lot.
- the hydrolysis may be carried out at various pH values comprised between 9 and 13. However, SBP yields will decrease at lower pH. Furthermore, depending on the RBM nature, in order to increase the product yield, it may be necessary to increase the reaction temperature up to 200 °C, working under autogenous pressure as required by the reaction temperature.
- the SBP obtained by the hydrolysis/membrane separation process are precipitated from the SOS solution at pH ⁇ 4 or, if obtained in solid form, they are washed with HC1 at 1/2-1/4 solid/liquid weight/volume ratio, depending upon the used HC1 concentration.
- the solid phase is washed with water until the collected washings have pH above 3.
- the solid phase is afterwards washed with concentrated HF at 1/4 solid/liquid weight/volume ratio, then washed with water to pH 3 and finally dried.
- the SBP obtained by the hydrolysis/precipitation process are washed by the same procedure reported above for the solid products sourced from the membrane separation/precipitation process.
- the mineral elements concentration of SBP are obtained after mineralization of the sample with HNO 3 -HF at 1:3 in v/v ratio and analyzed by atomic absorption spectroscopy.
- the C and N concentration are obtained with C. Erba NA-2100 type microanalyzer .
- the content of carboxylic and phenol groups is determined by potentiometric titration as follows. Deionized water is boiled under nitrogen flux to remove dissolved carbon dioxide. This water is used for sample preparation. The SBP sample is dissolved at 0,6 g L "1 concentration in 1 N KOH. The pH D.13 resulting solution is titrated with IN HC1. A similar titration is performed on a blank sample which does contain any SBP, but contains the same alkali amount as the SBP sample. The titration is performed with an automatic instrument such as the Cryson Compact having a resolution of 1 ⁇ titrant. In this condition, one obtains pH vs. titrant volume curves showing two inflection points. The COOH e PhOH concentration is calculated from these curves according to Graam method (Brunelot e coll., Chemosphere 1989, 19, 1413-1419).
- the determination of the concentration of C types and functional groups is performed as follows. Solid-state 13C- NMR spectra are acquired at 67.9 MHz on a JEOL GSE 270 spectrometer equipped with a Doty probe. The cross- polarization magic angle spinning (CPMAS) technique is employed and for each spectrum about 10 4 free induction decays is accumulated. The pulse repetition rate is set at 0.5 s, the contact time at 1 ms, the sweep width is 35 KHz and MAS is performed at 5 kHz. Under these conditions, the NMR technique provides quantitative integration values in the different spectral regions. Signals in the 13C NMR spectra are identified based on chemical shift referred to tetramethylsilane .
- CPMAS cross- polarization magic angle spinning
- Signals' assignment as a function of the resonance range are: 0-53 ppm aliphatic C, 53-63 ppm O-Me or N-alkyl C, 63-95 ppm O-alkyl C, 95-110 ppm di-O-alkyl C, 110-140 aromatic C, 140-160 ppm phenol or phenyl ether C, 160-185 carboxyl C, 185-215 keto C. Signals' band areas are measured and -assumed to correspond to the relative mole/mole concentration of the above identified functional groups.
- Soil contaminated by undesired organics and metals, is treated with SBP water solution at 0,01-1 SBP dry matter/soil ratio and 5-10 water/soil ratio.
- the solution and soil are held in contact until the partition equilibrium is reached; i.e. until the contaminant concentration in the water phase does not change anymore with time.
- the solution is the separated from " the soil phase by centrifugation and/or filtration.
- the soil sample may need to be washed repeatedly with fresh solution aliquots until the contaminant concentration in the soil is below the desired concentration.
- the recovered washing aliquots are collected together and processed by precipitation or membrane filtration.
- the SBP solution is acidified with a mineral acid to pH ⁇ 4 to yield a precipitate containing the contaminant (C) bonded to SBP (SBPC-PR) , which is centrifuged and separated from the liquid phase.
- C contaminant
- SBPC-PR SBP-PR
- SBPC-PR may be incinerated to remove all organics, and the residual mineral product may be recycled to further specific uses.
- the acid liquid phase is used again to precipitate other BPSC-PR obtained from the washings of other soil aliquots.
- the recovered SBP solution containing the contaminant washed out from the soil is conveyed to an ultrafiltration membrane with 5 kDalton cut off, applying 4 and 2 bar inlet and outlet membrane pressure respectively, until the retentate (SBPC-RUF) volume is reduced to 25 % or less relatively to the starting membrane feed volume.
- the SBPC-RUF may then be dried and burned as the above SBPC-PR.
- the permeate (PUF) is used to make up fresh SBP washing solution to use for treating other contaminated soil aliquots.
- This soil washing process may be carried out in continuous mode, by adequately setting the soil/solution contact time depending on the type of soil and contaminant to treat.
- the present invention covers a wide variety of SBP products, which are available thanks to the variety of available biowastes.
- the expert/potential user in the field has therefore a wide range of available products to tailor its product choice and to optimize the washing process according to the type of soil to be treated.
- SBP SBP and, e related process, for remediation of ground waters or industrial effluents contaminated by undesired organics and metals.
- Ground waters or industrial effluents contaminated by undesired organics and metals are added with SBP in solid or water solution form to yield a final 0,1-10 % SBP solution.
- This solution is treated by precipitation or membrane filtration as describe above. Optimizing the process parameters, such as SBP concentration and contaminant-SBP contact time it is possible to achieve 99 % abatement of contaminant, either by precipitation and/or ultrafiltration.
- the final ammonia concentration . in the fermentation liquor and/or in the gas phase will result more than 20-30 % lower relative to the same process carried out in the absence of SBP.
- a suspension containing 3 % of organic humid fraction of urban refuse from separate source collection undergoing anaerobic fermentation in a continuous reactor kept at 55 °C, run in the stationary state yields biogas with less than 0.5 ppm ammonia, 35 % methane e 15 % carbon dioxide, and the digestate liquor containing 1350 mg IT 1 ammonia and 1520 mg L "1 total Kjeldhal nitrogen in solution.
- Example a In vitro fermentation of animal feed containing protein in the presence of cecal content from slaughtered pigs.
- the following materials are used. 1) 11 % SPB water solution. 2) Standard feed for. pigs. This material is pre- digested to simulate ileal digestion by incubation in acid pepsin solution at 37 °C for 4 h, followed by incubation in pancreatin solution at pH 7.5 and 37 °C for 4 h. After enzymatic digestion, the preparation is centrifuged, washed twice with distilled water, centrifuged, and dried at 60°C overnight. The pre-digested fermentation feed substrate is characterized by the following analytical data as % w/w referred to dry matter: crude protein 4.44, crude fiber 8.68, crude fats 4.96, and starch 45.72. 3) Cecal content collected from pigs immediately after slaughtering and filtered before use. This material is used as incubation liquor.
- the SBP solutions, the feed substrate and the cecal content are used to prepare the fermentation liquors diluted with McDougall buffer. These contain 0.40 % feed substrate, ⁇ 31 % cecal content, 60 % buffer, 0-1-0.2 % SBP. The final pH of the freshly prepared fermentation liquor is 6.5.
- Example b In vivo animal growth test with diet containing protein feed added with SBP.
- Such free functional groups are desirable in some cases, as in soil washing, due to the fact that they have enhanced metal sequestering capacity compared to the same groups bonded to ' the mineral part in the sourcing SBP.
- these same free functionalities may complex the oligo-elements which are necessary in the animal diet and make them less available for the animal metabolism. In this fashion, they are likely to cause decreased growth rate and/or negative metabolic effects in the animal.
- the present invention covers a wide variety of SBP, whose composition depends on the sourcing material and on the process by which they are obtained.
- the expert/potential user in the field has therefore a large amount of opportunities to chose the SBP most suitable for the intended use, and so to optimize experimental conditions for best results.
- Table 1 ingredients except molasses, soybean oil, vitamins and SBP, are mixed in enough quantities for the preparation of finished total 15 kg feed. The mix is divided in three aliquots. The first is used as control. The other two are added with 5 and 10 % SBP respectively. All three aliquots are made into pellets. The products are tested for resistance to compression and shear, yielding the following results:
- Compressive strenght control 442 newton, SBP 5 % 561 newton, SBP 10 % 505 newton.
- the SBP binding property is particularly effective for the manufacture of objects containing inorganic oxides, such as silica and the oxides of magnesium, titanium, calcium, aluminum e iron. With these oxides the silica bonded to the SBP functional groups will react to yield the following SBP-Si-O-M condensation products, where M is a metal atom. For example, adding SBP to a metal oxide or to a mix of different metal oxides in water suspension at 30 % suspended solid concentration, having 2-10 w/w metal oxide/SBP ratio, followed by drying, will yield a solid object which takes the form of the container in which the product preparation is carried out.
- inorganic oxides such as silica and the oxides of magnesium, titanium, calcium, aluminum e iron.
- This solid object calcined at 600-800 °C, acquires greater mechanical strength than that of the same object obtained with the same metal oxides' mix, but in the absence of SBP.
- Use of SBP at doses adequate to promote plant photosynthesis and increase leaf chlorophyll content, and plants growth rate and productivity.
- an SBP solution having 10.4 pH, and 14.2 % dry matter and 10 % organic matter concentration values.
- the example demonstrates the effect of the SBP dose applied to soil for the cultivation of red pepper.
- the cultivation trial is performed according to a randomized experimental design with three replicates comprising the control soil (no SBP treatment) compared to the same soil treated with 6 SBP doses at 50, 250, 500, 1000, 2500 e 5000 kg ha "1 .
- Indicators of effects on plant health and growth are plant vigor, height and diameter, and leaf chlorophyll ' content. Total and commercial fruit production, and fruit quality parameters are also measured.
- enhancement chlorophyll leaf production due to the soil treatment with SBP is due to the capacity of SBP to absorb light and promote water splitting which generates OH radicals. These radicals catalyze the complex photosynthesis reactions, either by the nature of the SBP organic phase and by the presence of the SBP mineral component. Particularly, Mg is essential component of chlorophyll molecular structure. Fe is known for its photo-Fenton effect. The other mineral elements are well known plant nutrients. The role of the SBP organic components may likely be due to its water solubility and capacity to keep the above inorganic elements in solution at soil pH. In this fashion the SBP would be carrier of the mineral elements in solutions and ease out their transfer from soil to the plant, where they can play their effects.
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IT001192A ITTO20111192A1 (en) | 2011-12-22 | 2011-12-22 | BIO-POLYMERS ISOLATED BY RESIDUAL BIOMASSES AND BY FOSSILS, RELATED PRODUCTION PROCEDURES AND USES |
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IT201900010674A1 (en) | 2019-07-02 | 2021-01-02 | Hysytech Srl | PROCESS FOR THE ENHANCEMENT OF ORGANIC WASTE AND PRODUCTS OBTAINED THROUGH THE PROCESS |
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