ITMI20121707A1 - PROCEDURE FOR NEUTRALIZATION THROUGH CO2 OF HIGH-PH DIGESTATES AND LOW NITROGEN CONTENT - Google Patents
PROCEDURE FOR NEUTRALIZATION THROUGH CO2 OF HIGH-PH DIGESTATES AND LOW NITROGEN CONTENT Download PDFInfo
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- ITMI20121707A1 ITMI20121707A1 IT001707A ITMI20121707A ITMI20121707A1 IT MI20121707 A1 ITMI20121707 A1 IT MI20121707A1 IT 001707 A IT001707 A IT 001707A IT MI20121707 A ITMI20121707 A IT MI20121707A IT MI20121707 A1 ITMI20121707 A1 IT MI20121707A1
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- process according
- nitrogen
- digestate
- ammonia
- sulfuric acid
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 29
- 238000006386 neutralization reaction Methods 0.000 title claims description 10
- 230000008569 process Effects 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- 239000002689 soil Substances 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 11
- 235000010216 calcium carbonate Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 230000029087 digestion Effects 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 239000001166 ammonium sulphate Substances 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- 230000000696 methanogenic effect Effects 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 239000001120 potassium sulphate Substances 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 101100443249 Caenorhabditis elegans dig-1 gene Proteins 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- QUPVPSAQYXGFCJ-UHFFFAOYSA-N [N].S(O)(O)(=O)=O Chemical compound [N].S(O)(O)(=O)=O QUPVPSAQYXGFCJ-UHFFFAOYSA-N 0.000 claims 1
- 239000006096 absorbing agent Substances 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 239000012256 powdered iron Substances 0.000 claims 1
- 102100026139 DNA damage-inducible transcript 4 protein Human genes 0.000 description 6
- 101000912753 Homo sapiens DNA damage-inducible transcript 4 protein Proteins 0.000 description 6
- 239000012620 biological material Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- -1 acidic Substances 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 101100085126 Rattus norvegicus Ptgr1 gene Proteins 0.000 description 2
- 101100443250 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) DIG1 gene Proteins 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 240000004658 Medicago sativa Species 0.000 description 1
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- PNNCWTXUWKENPE-UHFFFAOYSA-N [N].NC(N)=O Chemical compound [N].NC(N)=O PNNCWTXUWKENPE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009418 agronomic effect Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000013872 defecation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 244000005706 microflora Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001863 plant nutrition Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002364 soil amendment Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/40—Treatment of liquids or slurries
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/50—Treatments combining two or more different biological or biochemical treatments, e.g. anaerobic and aerobic treatment or vermicomposting and aerobic treatment
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Description
DESCRIZIONE DESCRIPTION
Forma oggetto del presente trovato un procedimento per la neutralizzazione di digestati ad elevato pH e basso contenuto di azoto. The present invention relates to a process for the neutralization of digestates with a high pH and low nitrogen content.
E' noto, nel settore tecnico del trattamento dei suoli agrari che i materiali biologici derivati dalla digestione anaerobica metanogenica (noti anche con il termine di digestati) possono rappresentare un valido contributo all'ammendamento dei terreni ed alla nutrizione delle piante in quanto, oltre alla sostanza organica, tali materiali contengono anche considerevoli quantità di azoto, fosforo, potassio, calcio e zolfo. It is known in the technical sector of the treatment of agricultural soils that biological materials derived from methanogenic anaerobic digestion (also known as digestates) can represent a valid contribution to soil amendment and plant nutrition as, in addition to organic substance, these materials also contain considerable quantities of nitrogen, phosphorus, potassium, calcium and sulfur.
Mediamente i digestati, derivanti da materiali biologici trattati con tecnologie per liquidi, contengono una percentuale di sostanza secca compresa fra l'l% ed il 10% che dipende dalla tipologia dei materiali di partenza che subiscono la digestione anaerobica; esistono tuttavia anche trattamenti definiti "dry", che generano digestati con una percentuale di sostanza secca anche superiore al 35%. On average, digestates, deriving from biological materials treated with liquid technologies, contain a percentage of dry matter between 1% and 10% which depends on the type of starting materials that undergo anaerobic digestion; however, there are also treatments defined as "dry", which generate digestates with a percentage of dry matter even higher than 35%.
Con specifico riferimento all'azoto à ̈ anche noto che la quantità di azoto totale contenuta in un digestato à ̈ praticamente la stessa contenuta nel materiale biologico originario e che il totale dell'azoto à ̈ costituito da una parte organica e da una parte inorganica. With specific reference to nitrogen, it is also known that the quantity of total nitrogen contained in a digestate is practically the same as that contained in the original biological material and that the total nitrogen consists of an organic part and an inorganic part.
La quota inorganica à ̈ rappresentata per la maggior parte da azoto ammoniacale, ma comprende, anche se in minima parte, azoto nitrico e nitroso. L'azoto ureico fa parte dell'azoto organico. The inorganic share is represented for the most part by ammoniacal nitrogen, but includes, even if in a minimal part, nitric and nitrous nitrogen. Urea nitrogen is part of organic nitrogen.
In dettaglio l'azoto totale à ̈ mediamente compreso fra 1% e 6%, espresso sulla sostanza secca e la frazione ammoniacale à ̈ mediamente compresa fra 50% e 80% dell'azoto totale. In detail, the total nitrogen is on average between 1% and 6%, expressed on the dry matter and the ammonia fraction is on average between 50% and 80% of the total nitrogen.
L'azoto nitrico e nitroso sono presenti in percentuali non significative rispetto al totale. L'elevata presenza di azoto, nel caso di impiego dei digestati su superfici agricole ridotte, può tuttavia generare problematiche negative per l'ambiente, quali l'inquinamento delle falde idriche e l'eutrofizzazione dei mari; sono stati pertanto messi a punto procedimenti di trattamento dei digestati atti a ridurre la percentuale di azoto presente al loro interno tramite trasformazione dell'azoto organico in azoto ammoniacale e successiva estrazione dell'ammoniaca con formazione di solfato di ammonio. Nitric and nitrous nitrogen are present in insignificant percentages with respect to the total. The high presence of nitrogen, in the case of the use of digestates on small agricultural surfaces, can however generate negative problems for the environment, such as pollution of water tables and eutrophication of the seas; therefore, digestate treatment procedures have been developed to reduce the percentage of nitrogen present in them by transforming organic nitrogen into ammoniacal nitrogen and subsequent extraction of ammonia with the formation of ammonium sulphate.
Sebbene funzionali, tali trattamenti generano tuttavia un digestato residuo che presenta normalmente un pH>10 che ne riduce drasticamente la spandibilità sui terreni agricoli. Although functional, these treatments nevertheless generate a residual digestate which normally has a pH> 10 which drastically reduces its spreadability on agricultural land.
Si pone pertanto il problema tecnico di mettere a punto un procedimento per il trattamento di digestati ad elevato pH il quale sia in grado di generare miscele atte ad essere impiegate come correttivi di suoli agrari. The technical problem therefore arises of developing a process for the treatment of high pH digestates which is capable of generating mixtures suitable for use as corrective for agricultural soils.
Nell'ambito di tale problema tecnico si desidera anche che il procedimento sia applicabile a digestati risultanti da processi di riduzione del contenuto di azoto applicati a prodotti della digestione anaerobica metanogenica di biomasse. Within the scope of this technical problem, it is also desired that the process be applicable to digestates resulting from nitrogen content reduction processes applied to products of the methanogenic anaerobic digestion of biomass.
Tali risultati sono ottenuti secondo il presente trovato da un procedimento di neutralizzazione di digestati secondo le caratteristiche di rivendicazione 1. These results are obtained according to the present invention by a digestate neutralization process according to the characteristics of claim 1.
Maggiori dettagli potranno essere rilevati dalla seguente descrizione di un esempio non limitativo di attuazione dell'oggetto del presente trovato effettuata con riferimento ai disegni allegati, in cui si mostra: More details can be found from the following description of a non-limiting example of embodiment of the object of the present invention made with reference to the attached drawings, which show:
in figura 1 : uno schema a blocchi delle sequenze di processo del procedimento secondo il presente trovato ; in figure 1: a block diagram of the process sequences of the process according to the present invention;
in figura 2 : uno schema a blocchi delle sequenze di processo del procedimento secondo il presente trovato con fasi preliminari di ottenimento del digestato a basso contenuto di azoto. in figure 2: a block diagram of the process sequences of the process according to the present invention with preliminary steps for obtaining the digestate with a low nitrogen content.
Come illustrato in fig.l il procedimento di trattamento per digestati DIG2 con pH>10 e contenuto totale (sulla sostanza secca) di Azoto<0,12% e Calcio>25,8% comprende sostanzialmente una fase di neutralizzazione del digestato DIG2 stesso tramite aggiunta di anidride carbonica C02con generazione dì una miscela di sostanza organica e carbonato di calcio CaC03utilizzabile come correttivo e/o ammendante di suoli agrari, particolarmente suoli acidi, sodici ed argillosi. As illustrated in Fig. 1, the treatment process for DIG2 digestates with pH> 10 and total content (on dry matter) of Nitrogen <0.12% and Calcium> 25.8% substantially includes a neutralization step of the DIG2 digestate itself through addition of carbon dioxide C02 with generation gives a mixture of organic substance and calcium carbonate CaC03 usable as corrective and / or improver of agricultural soils, particularly acidic, sodium and clayey soils.
Più in dettaglio, nel digestato DIG2, sottoposto a neutralizzazione, gli ioni Ca<+>e OH<'>si combinano con l'anidride carbonica introdotta generando carbonato di calcio CaC03. More in detail, in the DIG2 digestate, subjected to neutralization, the Ca <+> and OH <'> ions combine with the carbon dioxide introduced to generate calcium carbonate CaC03.
Secondo una forma preferita di attuazione del metodo la quantità di C02introdotta à ̈ compresa tra 200 e 350g preferibilmente tra 250 e 300g per Kg di sostanza secca. According to a preferred embodiment of the method, the quantity of C02 introduced is between 200 and 350g, preferably between 250 and 300g per kg of dry substance.
L'introduzione di anidride carbonica à ̈ effettuata tramite insufflazione in quantità tale da portare il digestato DIG2 prossimo alla neutralità (7<pB<8). The introduction of carbon dioxide is carried out by insufflation in such a quantity as to bring the digestate DIG2 close to neutrality (7 <pB <8).
Da prove sperimentali effettuate si à ̈ verificato che un effetto positivo nella correzione dei suoli agrari viene determinato dall'uso di miscele risultanti dal trattamento di neutralizzazione secondo il presente trovato che contengano quantità non inferiori al 28% in peso di ossido di calcio CaO, sul peso totale della sostanza secca contenuta nella miscela. From experimental tests carried out it has been verified that a positive effect in the correction of agricultural soils is determined by the use of mixtures resulting from the neutralization treatment according to the present invention which contain quantities not less than 28% by weight of calcium oxide CaO, on the total weight of the dry substance contained in the mixture.
Risulta pertanto come il procedimento di neutralizzazione secondo il presente trovato consenta di ottenere una miscela di sostanza organica e in particolare di materiali biologici idrolizzati e carbonato di calcio la quale rientra nella definizione di "carbonato di calcio di defecazione" che à ̈ considerato un prodotto per uso agricolo come correttivo di terreni acidi, sodici ed argillosi. It therefore appears that the neutralization process according to the present invention allows to obtain a mixture of organic substance and in particular of hydrolyzed biological materials and calcium carbonate which falls within the definition of "defecation calcium carbonate" which is considered a product for agricultural use as a corrective for acidic, sodic and clayey soils.
Trattandosi di un materiale costituzionalmente alcalino il digestato neutralizzato secondo il trovato costituisce un idoneo correttivo per terreni con reazione acida e la sua efficacia à ̈ funzione di alcune caratteristiche del prodotto tra le quali: Since it is a constitutionally alkaline material, the neutralized digestate according to the invention constitutes a suitable corrective for soils with acid reaction and its effectiveness is a function of some characteristics of the product, including:
+) il comportamento chimico dei componenti prevalenti; trattandosi di un sale, si determina una azione fondamentalmente dovuta a fenomeni di idrolisi salina e/o di assorbimento selettivo da parte delle piante, per cui opera in modo più lento e prolungato dei prodotti contenenti acidi e basi; ) l'elevato grado di finezza del correttivo favorisce la maggiore reattività ed efficacia di azione nel suolo trattato; +) the chemical behavior of the main components; since it is a salt, an action is determined basically due to phenomena of saline hydrolysis and / or selective absorption by plants, for which it operates in a slower and longer way than products containing acids and bases; ) the high degree of refinement of the corrective favors greater reactivity and effectiveness of action in the treated soil;
+) il potere tampone, espresso dal complesso di scambio del terreno e, in misura minore, la composizione della frazione minerale della soluzione circolante hanno un intrinseco peso per compensare le variazioni di pH indotte dal correttivo . +) the buffering power, expressed by the soil exchange complex and, to a lesser extent, the composition of the mineral fraction of the circulating solution have an intrinsic weight to compensate for the pH variations induced by the corrective.
Come detto l'uso del correttivo secondo il trovato à ̈ rivolto in particolare ai seguenti suoli: terreni sodici: sono quelli con alcalinità di assorbimento dovuta ad eccesso di sodio, nel complesso di scambio e di sali di sodio a idrolisi alcalina nella soluzione circolante (carbonati e bicarbonati) . As mentioned, the use of the corrective agent according to the invention is aimed in particular at the following soils: sodium soils: those with alkalinity of absorption due to excess sodium, in the exchange complex and sodium salts with alkaline hydrolysis in the circulating solution ( carbonates and bicarbonates).
terreni acidi: in questi terreni l'idrogeno libero nella soluzione circolante, ma, soprattutto, quello legato ai colloidi minerali ed organici (idrogeno di scambio) determina il livello di acidità . Questa à ̈ causa di una serie di conseguenze negative fra cui : acid soils: in these soils the free hydrogen in the circulating solution, but, above all, that linked to mineral and organic colloids (exchange hydrogen) determines the level of acidity. This causes a number of negative consequences including:
-) la ridotta disponibilità di elementi nutritivi (Ca,Mg,K) e la scarsa assimilabilità del fosforo; -) l'inibizione della microflora batterica con conseguente rallentamento dei processi di nitrificazione ; -) the reduced availability of nutritional elements (Ca, Mg, K) and the poor assimilability of phosphorus; -) inhibition of bacterial microflora with consequent slowdown of nitrification processes;
le condizioni di anaerobicità (cattiva strutturazione del terreno, scarsa mineralizzazione della sostanza organica). conditions of anaerobicity (poor soil structure, poor mineralization of the organic substance).
Tra le colture erbacee che maggiormente risentono in modo negativo di pH acidi si possono indicare erba medica, orzo, frumento e barbabietola da zucchero e risultano mediamente sensibili anche soia e girasole. Among the herbaceous crops that are most negatively affected by acid pH, we can indicate alfalfa, barley, wheat and sugar beet and soy and sunflower are also on average sensitive.
Oltre all'azione correttiva vera e propria, il digestato neutralizzato secondo il trovato determina anche risultati significativi quando usato come ammendante in quanto capace di migliorare le caratteristiche fisiche, chimiche e meccaniche del suolo a tutto beneficio dell'attività biologica che vi insiste. In addition to the actual corrective action, the neutralized digestate according to the invention also determines significant results when used as a soil improver as it is capable of improving the physical, chemical and mechanical characteristics of the soil to the full benefit of the biological activity that insists on it.
Quindi l'apporto dello ione calcio, anche nei terreni neutri, debolmente alcalini, argillosi e con problemi di struttura, migliora diversi importanti parametri, quali la stabilità di struttura, la lavorabilità , la capacità di ritenzione idrica. Therefore the contribution of the calcium ion, even in neutral, weakly alkaline, clayey soils and with structural problems, improves several important parameters, such as the stability of the structure, the workability, the water retention capacity.
Oltre a quanto sopra il digestato neutralizzato con C02 risulta efficace per una azione fertilizzante diretta sulle colture. In addition to the above, the digestate neutralized with C02 is effective for a direct fertilizing action on crops.
Infatti può essere molto utile, per il mantenimento delle dotazioni di nutritivi, la capacità di riequilibrare il rapporto dei cationi di scambio fra calcio e magnesio, per quei terreni troppo ricchi di magnesio, in quanto derivanti da substrati pedologici di prevalente composizione dolomitica ( con carbonati doppi di calcio e magnesio), invece che calcarea (carbonati di calcio) . In fact, the ability to rebalance the ratio of exchange cations between calcium and magnesium can be very useful for maintaining the nutrient supply, for those soils too rich in magnesium, as they derive from soil substrates of prevalent dolomitic composition (with carbonates doubles of calcium and magnesium), instead of limestone (calcium carbonates).
Inoltre, il materiale biologico di origine, dopo il processo di idrolisi con calce e successiva precipitazione con anidride carbonica, apporta degli amminoacidi residuali con lenta mineralizzazione, disponibile per le colture, insieme ad una quota di carbonio organico utilissima per le proprietà fisico meccaniche già accennate . Furthermore, the biological material of origin, after the hydrolysis process with lime and subsequent precipitation with carbon dioxide, brings residual amino acids with slow mineralization, available for crops, together with a share of organic carbon very useful for the physical-mechanical properties already mentioned. .
Secondo una forma preferita di attuazione del procedimento il digestato DIG2 da neutralizzare viene ottenuto da un digestato iniziale derivante dalla digestione anaerobica metanogenica di una biomassa tramite un processo di riduzione della quantità di azoto comprendente le seguenti fasi: a) conversione dell'azoto organico in azoto ammoniacale tramite attacco con acido solforico (H2S04) in presenza di solfato di potassio. According to a preferred embodiment of the process, the DIG2 digestate to be neutralized is obtained from an initial digestate deriving from the methanogenic anaerobic digestion of a biomass through a nitrogen quantity reduction process comprising the following steps: a) conversion of organic nitrogen into nitrogen ammoniacal by etching with sulfuric acid (H2S04) in the presence of potassium sulphate.
Il digestato DIG1 viene pompato in un primo reattore in acciaio inox e mantenuto in agitazione. Quindi viene introdotto acido solforico H2S04fino a raggiungere pH compreso fra 1 e 2. DIG1 digestate is pumped into a first stainless steel reactor and kept under agitation. Then H2SO4 sulfuric acid is introduced until it reaches pH between 1 and 2.
Preferìbilmente in tale fase sono anche aggiunti potassio solfato in quantità compresa tra il 5% e il 10% in peso per Kg di sostanza secca, allo scopo di favorire la mineralizzazione dell'Azoto organico e ferro metallico in polvere in quantità compresa tra il 0,25% e il 0,5% in peso per Kg di sostanza secca, per la riduzione dei nitrati NO3 e dei nitriti N02ad azoto ammoniacale. Preferably, potassium sulphate is also added in this phase in a quantity between 5% and 10% by weight per kg of dry substance, in order to favor the mineralization of organic nitrogen and metallic iron powder in quantities ranging from 0.25% and 0.5% by weight per kg of dry matter, for the reduction of NO3 nitrates and NO2 nitrites to ammonia nitrogen.
Secondo forme preferite di attuazione tale fase viene attuata sotto le seguenti condizioni: According to preferred embodiments, this step is carried out under the following conditions:
La massa à ̈ mantenuta riscaldata ad una temperatura maggiore di 60°C, preferìbilmente compresa tra 70° e 75° C; The mass is kept heated to a temperature higher than 60 ° C, preferably between 70 ° and 75 ° C;
per un tempo di reazione di circa 60 minuti. for a reaction time of about 60 minutes.
Questo primo trattamento permette dì idrolizzare le proteine presenti, liberando l'azoto organico che à ̈ convertito in ammoniacale. This first treatment allows to hydrolyze the proteins present, releasing the organic nitrogen which is converted into ammonia.
b) condizionamento del digestato con innalzamento del pH a valori maggiori di 10, preferibilmente tramite l'aggiunta di ossido di calcio CaO, e carbonato di calcio in polvere, mantenendo una temperatura di processo compresa fra 50 e 80°C , preferibilmente compresa tra 70 e 75 °C; b) conditioning of the digestate with raising the pH to values greater than 10, preferably by adding calcium oxide CaO, and calcium carbonate in powder, maintaining a process temperature between 50 and 80 ° C, preferably between 70 and 75 ° C;
l'ossido di calcio viene aggiunto in quantità compresa tra 500 e 650 grammi, preferibilmente tra 560 e 600 grammi per Kg di sostanza secca del digestato (DIG 1); calcium oxide is added in quantities ranging from 500 to 650 grams, preferably from 560 to 600 grams per kg of dry matter of the digestate (DIG 1);
il carbonato di calcio in polvere viene aggiunto per la parziale neutralizzazione dell'acido solforico utilizzato nella fase a) per la conversione dell'azoto organico in azoto ammoniacale . the powdered calcium carbonate is added for the partial neutralization of the sulfuric acid used in step a) for the conversion of organic nitrogen into ammoniacal nitrogen.
c) estrazione di ammoniaca in fase gassosa per la riduzione della quantità di azoto presente nel digestato; l'estrazione avviene all'interno di un reattore con: c) extraction of ammonia in the gaseous phase to reduce the quantity of nitrogen present in the digestate; the extraction takes place inside a reactor with:
+ insufflazione di aria atmosferica mediante una soffiante, per generare un flusso di bolle che permettano il trascinamento dell'ammoniaca al di fuori del reattore, e una contemporanea aspirazione, tramite una seconda soffiante, posta a valle del reattore, della corrente d'aria contenente l'ammoniaca che si libera dalla massa; introduzione di acido solforico, utilizzato come liquido circolante, in una colonna di assorbimento posta fra il reattore e la soffiante di aspirazione ; + insufflation of atmospheric air by means of a blower, to generate a flow of bubbles that allow the ammonia to be dragged out of the reactor, and a simultaneous suction, by means of a second blower, located downstream of the reactor, of the air stream containing ammonia released from the mass; introduction of sulfuric acid, used as a circulating liquid, into an absorption column placed between the reactor and the suction blower;
+ nella stessa colonna risale controcorrente l'ammoniaca liberata dalla massa, la quale si combina con l'acido solforico H2S04formando solfato di ammonio in soluzione che viene estratto, immagazzinato per l'utilizzo agronomico e sostituito con altro acido solforico per la continuazione del processo. + in the same column the ammonia released from the mass rises against the current, which combines with the sulfuric acid H2S04 forming ammonium sulphate in solution which is extracted, stored for agronomic use and replaced with other sulfuric acid for the continuation of the process.
Al termine del trattamento, il digestato iniziale DIG1 Ã ̈ diventato un digestato intermedio DIG2 fortemente alcalino (pH>10) e praticamente privo di azoto N<0,12% (ad eccezione di una minima frazione di azoto organico che non avesse reagito} e con contenuto di calcio Ca mediamente maggiore del 25,8% da avviare alla successiva fase di neutralizzazione secondo il presente trovato. At the end of the treatment, the initial digestate DIG1 became an intermediate digestate DIG2 strongly alkaline (pH> 10) and practically devoid of nitrogen N <0.12% (except for a small fraction of organic nitrogen that had not reacted} and with calcium Ca content on average greater than 25.8% to be sent to the subsequent neutralization step according to the present invention.
Benché descritta nel contesto di alcune forme di realizzazione e di alcuni esempi preferiti di attuazione dell'invenzione si intende che l'ambito di protezione del presente brevetto sia determinato solo dalle rivendicazioni che seguono. Although described in the context of some embodiments and some preferred examples of embodiment of the invention, it is intended that the scope of protection of the present patent is determined only by the following claims.
Claims (15)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2998277B1 (en) * | 2014-09-19 | 2019-03-20 | Syngen S.r.l. | Method for treating biological materials associated with the wastewater purification cycle |
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