IT202000025960A1 - PROCESS FOR THE ISOMERIZATION OF GLUCIDS IN HYDROXYMETHYLFURFURAL - Google Patents
PROCESS FOR THE ISOMERIZATION OF GLUCIDS IN HYDROXYMETHYLFURFURAL Download PDFInfo
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- IT202000025960A1 IT202000025960A1 IT102020000025960A IT202000025960A IT202000025960A1 IT 202000025960 A1 IT202000025960 A1 IT 202000025960A1 IT 102020000025960 A IT102020000025960 A IT 102020000025960A IT 202000025960 A IT202000025960 A IT 202000025960A IT 202000025960 A1 IT202000025960 A1 IT 202000025960A1
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- Italy
- Prior art keywords
- process according
- catalyst
- hydroxymethylfurfural
- isomerization
- metal
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 42
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims description 31
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims description 31
- 238000006317 isomerization reaction Methods 0.000 title claims description 17
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000010955 niobium Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 14
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 13
- 239000008101 lactose Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 150000001720 carbohydrates Chemical class 0.000 claims description 12
- 235000014633 carbohydrates Nutrition 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 229930182830 galactose Natural products 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000001476 alcoholic effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 101100173048 Mus musculus Mcat gene Proteins 0.000 description 5
- 229910019670 (NH4)H2PO4 Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910019804 NbCl5 Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002417 nutraceutical Substances 0.000 description 1
- 235000021436 nutraceutical agent Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Saccharide Compounds (AREA)
- Furan Compounds (AREA)
Description
Descrizione di Brevetto per Invenzione Industriale avente per titolo: Description of Patent for Industrial Invention having the title:
?PROCESSO PER L?ISOMERIZZAZIONE DI GLUCIDI IN IDROSSIMETILFURFURALE?. ?PROCESS FOR THE ISOMERIZATION OF GLUCIDS INTO HYDROXYMETHYLFURFURAL?.
DESCRIZIONE DESCRIPTION
La presente invenzione si riferisce ad un processo per l?isomerizzazione di glucidi in idrossimetilfurfurale. The present invention relates to a process for the isomerization of carbohydrates in hydroxymethylfurfural.
Negli ultimi anni ? particolarmente sentita la necessit? di sviluppare un?industria chimica sostenibile. In the last few years ? particularly felt the need? to develop a sustainable chemical industry.
Ci? ? dovuto a diversi fattori tra i quali l?esaurimento delle riserve di combustibili fossili, il costo elevato del petrolio, la necessit? di diminuire le emissioni di CO2, l?aumento della domanda energetica e le leggi ambientali sempre pi? restrittive. There? ? due to several factors including? the exhaustion of fossil fuel reserves, the high cost of oil, the need? to decrease CO2 emissions, the increase in energy demand and environmental laws more and more? restrictive.
In questo contesto, le biomasse e le materie prima di scarto derivanti da processi industriali hanno suscitato particolare interesse per la possibilit? di essere convertite in composti chimici, ossia le cosiddette ?molecole piattaforma?, utili per la produzione di numerosi prodotti applicabili in diversi campi industriali e tecnologici. In this context, biomass and waste raw materials deriving from industrial processes have aroused particular interest in the possibility to be converted into chemical compounds, i.e. the so-called ?platform molecules?, useful for the production of numerous products applicable in various industrial and technological fields.
Lo sviluppo di processi catalitici sostenibili e quindi la creazione di impianti industriali atti alla conversione delle suddette biomasse e/o materie prime di scarto, ? attualmente un?esigenza particolarmente sentita al fine di fornire un?alternativa alla petrolchimica. The development of sustainable catalytic processes and therefore the creation of industrial plants suitable for the conversion of the aforementioned biomass and/or waste raw materials, ? currently a particularly felt need in order to provide an alternative to petrochemicals.
Con particolare riferimento alla sintesi di ?molecole piattaforma?, i processi di sintesi di idrossimetilfurfurale sono di notevole interesse alla luce delle numerose applicazioni della suddetta molecola. With particular reference to the synthesis of ?platform molecules?, the synthesis processes of hydroxymethylfurfural are of considerable interest in the light of the numerous applications of the aforementioned molecule.
Tra le numerose applicazioni dell?idrossimetilfurfurale si annoverano l?impiego di idrossimetilfurfurale per la sintesi di acido furandicarbossilico, molecola di fondamentale importanza per la produzione di polietilenfuranoato, un?alternativa ecocompatibile al polietilentereftalato. Inoltre, l?idrossimetilfurfurale ? ampiamente impiegato, tramite conversione, per l?ottenimento di dimetilfurano molecola impiegabile come biocarburante. The numerous applications of hydroxymethylfurfural include the use of hydroxymethylfurfural for the synthesis of furandicarboxylic acid, a molecule of fundamental importance for the production of polyethylenefuranoate, an environmentally friendly alternative to polyethylene terephthalate. Furthermore, hydroxymethylfurfural ? widely used, through conversion, to obtain dimethylfuran, a molecule that can be used as a biofuel.
A ci? si aggiunge che l?idrossimetilfurfurale ? impiegabile anche nell?industria alimentare, farmaceutica e nutraceutica. To there? it is added that the? hydroxymethylfurfural? can also be used in the food, pharmaceutical and nutraceutical industries.
Attualmente, l?idrossimetilfurfurale viene sintetizzata a partire da scarti di origine vegetale mediante un procedimento che richiede condizioni di processo estreme, cio? presentanti condizioni di temperatura e pressione estremamente elevate. Currently, hydroxymethylfurfural is synthesized from waste of vegetable origin through a process that requires extreme process conditions, i.e. presenting extremely high temperature and pressure conditions.
Tali condizioni di processo influenzano sensibilmente la gestione energetica del procedimento di sintesi che presenta costi di gestione estremamente elevati, oltre che il costo del prodotto finale stesso anch?esso elevato. These process conditions significantly influence the energy management of the synthesis process which has extremely high management costs, as well as the cost of the final product itself, which is also high.
Il compito principale della presente invenzione ? quello di escogitare un processo per l?isomerizzazione di glucidi in idrossimetilfurfurale che presenti condizioni di processo blande, rispetto ai processi noti, riducendo notevolmente i costi di gestione energetica del processo stesso. The main task of the present invention ? that of devising a process for the isomerization of glucids in hydroxymethylfurfural which has mild process conditions, compared to known processes, considerably reducing the energy management costs of the process itself.
Uno scopo del presente trovato ? quello di escogitare un processo per l?isomerizzazione di glucidi in idrossimetilfurfurale che consenta di ridurre notevolmente il costo di vendita della suddetta molecola. A purpose of the present invention ? that of devising a process for the isomerization of glucids in hydroxymethylfurfural which allows to significantly reduce the sale cost of the aforesaid molecule.
Altro scopo del presente trovato ? quello di escogitare un processo per l?isomerizzazione di glucidi in idrossimetilfurfurale che consenta di superare i menzionati inconvenienti della tecnica nota nell?ambito di una soluzione semplice, razionale, di facile ed efficace impiego e dal costo contenuto. Another object of the present invention ? that of devising a process for the isomerization of glucides in hydroxymethylfurfural which allows the aforementioned drawbacks of the prior art to be overcome within the scope of a simple, rational, easy and effective to use and low-cost solution.
Gli scopi sopra esposti sono raggiunti dal presente processo per l?isomerizzazione di glucidi in idrossimetilfurfurale avente le caratteristiche di rivendicazione 1. The above objects are achieved by the present process for the isomerization of carbohydrates in hydroxymethylfurfural having the characteristics of claim 1.
Ulteriormente, gli scopi sopra esposti sono raggiunti dal catalizzatore per l?isomerizzazione di glucidi in idrossimetilfurfurale avente le caratteristiche di rivendicazione 13. Furthermore, the above objects are achieved by the catalyst for the isomerization of carbohydrates in hydroxymethylfurfural having the characteristics of claim 13.
Ancora, gli scopi sopra esposti sono raggiunti dall?uso di un fosfato metallico per l?isomerizzazione di glucidi in idrossimetilfurfurale avente le caratteristiche di rivendicazione 14. Again, the above objects are achieved by the use of a metal phosphate for the isomerization of carbohydrates in hydroxymethylfurfural having the characteristics of claim 14.
In un primo aspetto, la presente invenzione riguarda un processo per l?isomerizzazione di glucidi in idrossimetilfurfurale (HMF), comprendente le seguenti fasi. In a first aspect, the present invention relates to a process for the isomerization of carbohydrates in hydroxymethylfurfural (HMF), comprising the following steps.
Il processo comprende una fase di fornitura di: The process includes a supply phase of:
- almeno un glucide scelto dall?elenco comprendente: lattosio, glucosio, galattosio, fruttosio e saccarosio; e - at least one carbohydrate selected from the list comprising: lactose, glucose, galactose, fructose and sucrose; And
- almeno un catalizzatore comprendente almeno un fosfato metallico in cui il metallo ? scelto dall?elenco comprendente: niobio, zirconio, afnio, titanio, alluminio. - at least one catalyst comprising at least one metal phosphate in which the metal is chosen from the list including: niobium, zirconium, hafnium, titanium, aluminium.
Si specifica che nell?ambito della presente trattazione con il termine ?miscela?, impiegato nelle rivendicazioni e nella descrizione, si intendono sia miscele omogenee, ad esempio soluzioni liquide o solide, sia miscele eterogenee quali sospensioni di un particolato solido in un liquido o miscele solido-liquido in cui il solido sia in tutto o in parte sedimentato. Ulteriormente, con il termine ?mole? e ?rapporto molare? si fa riferimento sia a composti costituiti da molecole sia con riferimento ad atomi e ioni, tralasciando per questi ultimi i termini grammo-atomo o rapporto atomico, anche se pi? corretti scientificamente. It is specified that in the context of the present discussion the term "mixture", used in the claims and in the description, means both homogeneous mixtures, for example liquid or solid solutions, and heterogeneous mixtures such as suspensions of a solid particulate in a liquid or mixtures solid-liquid in which the solid is wholly or partially sedimented. Furthermore, with the term ?mole? and ?molar ratio? reference is made both to compounds consisting of molecules and with reference to atoms and ions, leaving out for the latter the terms gram-atom or atomic ratio, even if more? scientifically correct.
Inoltre, ? doveroso sottolineare che il processo in accordo con il presente trovato ? condotto in atmosfera inerte. Moreover, ? necessary to underline that the process in accordance with the present invention ? conducted in an inert atmosphere.
Ci? significa che il processo ? condotto, ad esempio, in atmosfera di azoto. Il processo in accordo con il presente trovato ? condotto in un reattore che, una volta sigillato, viene spurgato al fine di garantire la realizzazione di un ambiente inerte. There? does it mean that the process ? conducted, for example, in a nitrogen atmosphere. The process in accordance with the present invention ? conducted in a reactor which, once sealed, is purged in order to ensure the creation of an inert environment.
Tuttavia, non si esclude dall?ambito della presente trattazione che il processo sia condotto in atmosfera non inerte, cio? in presenza di altri gas come ad esempio ossigeno, aria, anidride carbonica. However, it is not excluded from the scope of this discussion that the process is conducted in a non-inert atmosphere, ie? in the presence of other gases such as oxygen, air, carbon dioxide.
Nella fattispecie, il glucide e il catalizzatore sono presenti in un rapporto molare compreso tra 1:0.01 e 1:1. In this case, the carbohydrate and the catalyst are present in a molar ratio between 1:0.01 and 1:1.
In accordo con una preferita forma di realizzazione il fosfato metallico comprende Niobio (Nb/P/O). In accordance with a preferred embodiment, the metal phosphate comprises Niobium (Nb/P/O).
In alternativa, il fosfato metallico comprende Zirconio (Zr/P/O). Alternatively, the metal phosphate comprises Zirconium (Zr/P/O).
Ulteriormente, in alternativa, il fosfato metallico comprende Afnio (Hf/P/O). Further, alternatively, the metal phosphate comprises Hafnium (Hf/P/O).
In aggiunta, alternativamente alle suddette forme di realizzazione del catalizzatore, il fosfato metallico comprende Titanio (Ti/P/O). Ancora, in alternativa, il fosfato metallico comprende Alluminio (Al/P/O). Successivamente, il procedimento comprende una fase di aggiunta di almeno un solvente di reazione ad ottenere una miscela di reazione. In addition, as an alternative to the above catalyst embodiments, the metal phosphate comprises Titanium (Ti/P/O). Again, alternatively, the metal phosphate comprises Aluminum (Al/P/O). Subsequently, the process comprises a step of adding at least one reaction solvent to obtain a reaction mixture.
Nel dettaglio, il solvente di reazione comprende almeno uno tra acqua ed un solvente organico. In detail, the reaction solvent comprises at least one of water and an organic solvent.
Ci? significa che la miscela di reazione comprende: There? means that the reaction mixture includes:
- acqua; o - water; or
- acqua ed un solvente organico; o - water and an organic solvent; or
- un solvente organico. - an organic solvent.
Preferibilmente, il solvente organico ? scelto dall?elenco comprendente: metil-tetraidrofurano, tetraidrofurano, n-butanolo e gamma-valerolactone. La presenza di acqua nella miscela di reazione assume peculiare importanza grazie alla sua facile separazione dal solvente organico. Preferably, the organic solvent ? selected from the list including: methyl tetrahydrofuran, tetrahydrofuran, n-butanol and gamma-valerolactone. The presence of water in the reaction mixture assumes particular importance due to its easy separation from the organic solvent.
L?acqua, dunque, essendo altamente polare, ? insolubile nella maggior parte dei solventi organici. The water, therefore, being highly polar, ? insoluble in most organic solvents.
Preferibilmente, il solvente organico e l?acqua sono presenti nella miscela di reazione con un rapporto molare compreso tra 1:1 e 4:1. Preferably, the organic solvent and water are present in the reaction mixture with a molar ratio between 1:1 and 4:1.
A questo punto, il processo in accordo con il presente trovato prevede il riscaldamento della miscela di reazione ad una temperatura superiore a 80?C. At this point, the process according to the present invention provides for the heating of the reaction mixture to a temperature higher than 80°C.
Preferibilmente, la miscela di reazione ? riscaldata ad una temperatura compresa tra 80?C e 200?C. Preferably, the reaction mixture is heated to a temperature between 80?C and 200?C.
Ulteriormente, il processo ? condotto a valori di pressione compresi tra 5 bar e 25 bar. Furthermore, the process ? conducted at pressure values between 5 bar and 25 bar.
A seguire, successivamente alla fase di riscaldamento, il processo comprende una fase di raffreddamento della miscela di reazione. Subsequently, after the heating step, the process comprises a cooling step of the reaction mixture.
Nel dettaglio, la fase di raffreddamento ? atta a consentire il raffreddamento della miscela di reazione fino al raggiungimento della temperatura ambientale. In detail, the cooling phase? adapted to allow the cooling of the reaction mixture until the ambient temperature is reached.
Si specifica che nell?ambito della presente trattazione con l?espressione ?temperatura ambientale? si fa riferimento ad una temperatura sostanzialmente pari a 20?C. It is specified that in the context of this discussion with the expression ?ambient temperature? reference is made to a temperature substantially equal to 20°C.
A questo punto, il processo comprende una fase di rigenerazione del catalizzatore in cui quest?ultimo ? essiccato termicamente ad una temperatura superiore a 200?C. At this point, the process includes a regeneration phase of the catalyst in which the latter is thermally dried at a temperature above 200?C.
Preferibilmente, il catalizzatore ? essiccato ad una temperatura superiore a 400?C, pi? preferibilmente tra 400?C e 600?C. Preferably, the catalyst ? dried at a temperature higher than 400?C, pi? preferably between 400?C and 600?C.
Utilmente, la fase di rigenerazione ? condotta per un tempo operativo sostanzialmente pari a 5 ore. Usefully, the regeneration phase? conducted for an operating time substantially equal to 5 hours.
Il processo in accordo con il presente trovato, presenta una resa in idrossimetilfurfurale (HMF) superiore a 20%. The process according to the present invention has a yield of hydroxymethylfurfural (HMF) higher than 20%.
? doveroso sottolineare che il processo in accordo con il presente trovato comprende una fase di preparazione, a sua volta, comprendente la precipitazione in ambiente acido del catalizzatore a partire da almeno un precursore metallico o per idrolisi e condensazione del precursore metallico. ? It must be emphasized that the process according to the present invention comprises a preparation step, in turn comprising the precipitation of the catalyst in an acid environment starting from at least one metal precursor or by hydrolysis and condensation of the metal precursor.
Preferibilmente, l?idrolisi e condensazione del precursore metallico avviene con metodo sol-gel. Preferably, the hydrolysis and condensation of the metal precursor occurs with the sol-gel method.
A titolo esemplificativo, si elencano qui di seguito le fasi di preparazione del catalizzatore. By way of example, the steps for preparing the catalyst are listed below.
ESEMPIO PREPARATIVO 1: PREPARATION EXAMPLE 1:
Catalizzatore Nb/P/O - PRECIPITAZIONE IN AMBIENTE ACIDO CON METODO IDROTERMALE Catalyst Nb/P/O - PRECIPITATION IN ACID ENVIRONMENT WITH HYDROTHERMAL METHOD
In un becher in teflon 25 ml di soluzione alcolica 0.4 M di H3PO4 vengono aggiunti lentamente a 25 ml di soluzione alcolica 0.2 M di NbCl5. In a Teflon beaker, 25 ml of 0.4 M alcoholic solution of H3PO4 are slowly added to 25 ml of 0.2 M alcoholic solution of NbCl5.
La miscela cos? ottenuta ? mantenuta sotto agitazione per 30 minuti. What is the mixture? obtained ? kept under stirring for 30 minutes.
Successivamente, in condizioni di agitazione continua, alla suddetta miscela viene aggiunta NH3 concentrata al 25% fino al raggiungimento di un pH pari a 2.6, ottenendo la formazione di un precipitato bianco. Subsequently, under conditions of continuous stirring, NH3 concentrated at 25% is added to the above mixture until a pH equal to 2.6 is reached, obtaining the formation of a white precipitate.
Il precipitato risultante viene filtrato e lavato diverse volte con etanolo. All?interno di un becher contenente una soluzione alcolica di esadecilammina 0.6M, viene aggiunto il precipitato bianco. The resulting precipitate is filtered and washed several times with ethanol. The white precipitate is added to a beaker containing an alcoholic solution of hexadecylamine 0.6M.
Alla suddetta miscela viene quindi aggiunto H3PO4 in una concentrazione in peso, valutata rispetto al peso complessivo della miscela stessa, sostanzialmente pari al 85% fino al raggiungimento di un pH sostanzialmente pari a 3.9. H3PO4 is then added to the above mixture in a concentration by weight, evaluated with respect to the total weight of the mixture itself, substantially equal to 85% until a pH substantially equal to 3.9 is reached.
Il gel risultante viene riscaldato in un?autoclave di teflon a 65?C per due giorni in pressione autogena. The resulting gel is heated in a Teflon autoclave at 65°C for two days under autogenous pressure.
A questo punto, il prodotto ottenuto ? filtrato, lavato con etanolo, essiccato a 120?C e calcinato in muffola in condizioni statiche ad una temperatura compresa tra 400?C e 600?C. At this point, the product obtained? filtered, washed with ethanol, dried at 120°C and calcined in a muffle under static conditions at a temperature between 400°C and 600°C.
La velocit? di riscaldamento ? sostanzialmente pari a 10?C/min per una durata sostanzialmente compresa tra 3 e 6 ore. The speed? of heating ? substantially equal to 10?C/min for a duration substantially between 3 and 6 hours.
ESEMPIO PREPARATIVO 2: PREPARATION EXAMPLE 2:
Catalizzatore Nb/P/O - PRECIPITAZIONE IN AMBIENTE ACIDO CON METODO IDROTERMALE e AGGIUNTA DI TEMPLANTE Catalyst Nb/P/O - PRECIPITATION IN ACID ENVIRONMENT WITH HYDROTHERMAL METHOD and ADDITION OF TEMPLANT
In un becher in teflon 25 ml di soluzione alcolica 0.4 M di H3PO4 vengono aggiunti lentamente a 25 ml di soluzione alcolica 0.2 M di NbCl5. In a Teflon beaker, 25 ml of 0.4 M alcoholic solution of H3PO4 are slowly added to 25 ml of 0.2 M alcoholic solution of NbCl5.
La miscela cos? ottenuta ? mantenuta sotto agitazione per 30 minuti. What is the mixture? obtained ? kept under stirring for 30 minutes.
Successivamente, in condizioni di agitazione continua, alla suddetta miscela viene aggiunta NH3 concentrata al 25% fino al raggiungimento di un pH pari a 2.6, ottenendo la formazione di un precipitato bianco. Subsequently, under conditions of continuous stirring, NH3 concentrated at 25% is added to the above mixture until a pH equal to 2.6 is reached, obtaining the formation of a white precipitate.
Il precipitato risultante viene filtrato e lavato diverse volte con etanolo. All?interno di un becher contenente una soluzione alcolica di esadecilammina 0.6M, viene aggiunto il precipitato bianco. The resulting precipitate is filtered and washed several times with ethanol. The white precipitate is added to a beaker containing an alcoholic solution of hexadecylamine 0.6M.
Alla suddetta miscela viene quindi aggiunto H3PO4 in una concentrazione in peso, valutata rispetto al peso complessivo della miscela stessa, sostanzialmente pari al 85% fino al raggiungimento di un pH sostanzialmente pari a 3.9. H3PO4 is then added to the above mixture in a concentration by weight, evaluated with respect to the total weight of the mixture itself, substantially equal to 85% until a pH substantially equal to 3.9 is reached.
Il gel risultante viene riscaldato in un?autoclave di teflon a 65?C per due giorni in pressione autogena. The resulting gel is heated in a Teflon autoclave at 65°C for two days under autogenous pressure.
A questo punto, il prodotto ottenuto ? filtrato, lavato con etanolo, essiccato a 120?C e calcinato in muffola in condizioni statiche ad una temperatura compresa tra 400?C e 600?C. At this point, the product obtained? filtered, washed with ethanol, dried at 120°C and calcined in a muffle under static conditions at a temperature between 400°C and 600°C.
La velocit? di riscaldamento ? sostanzialmente pari a 10?C/min per una durata sostanzialmente compresa tra 3 e 6 ore. The speed? of heating ? substantially equal to 10?C/min for a duration substantially between 3 and 6 hours.
ESEMPIO PREPARATIVO 3: PREPARATION EXAMPLE 3:
Catalizzatore Nb/P/O - PRECIPITAZIONE IN AMBIENTE ACIDO CON METODO IDROTERMALE e AGGIUNTA DI TEMPLANTE Catalyst Nb/P/O - PRECIPITATION IN ACID ENVIRONMENT WITH HYDROTHERMAL METHOD and ADDITION OF TEMPLANT
In un becher in teflon 25 ml di soluzione alcolica 0.4 M di H3PO4 vengono aggiunti lentamente a 25 ml di soluzione alcolica 0.2 M di NbCl5. In a Teflon beaker, 25 ml of 0.4 M alcoholic solution of H3PO4 are slowly added to 25 ml of 0.2 M alcoholic solution of NbCl5.
La miscela cos? ottenuta ? mantenuta sotto agitazione per 30 minuti. What is the mixture? obtained ? kept under stirring for 30 minutes.
Successivamente, in condizioni di agitazione continua, alla suddetta miscela viene aggiunta NH3 concentrata al 25% fino al raggiungimento di un pH pari a 2.6, ottenendo la formazione di un precipitato bianco. Subsequently, under conditions of continuous stirring, NH3 concentrated at 25% is added to the above mixture until a pH equal to 2.6 is reached, obtaining the formation of a white precipitate.
Il precipitato risultante viene filtrato e lavato diverse volte con etanolo. All?interno di un becher contenente una soluzione alcolica di cetiltrimetilammonio (CTAB) 0.6M, viene aggiunto il precipitato bianco. The resulting precipitate is filtered and washed several times with ethanol. The white precipitate is added to a beaker containing an alcoholic solution of cetyltrimethylammonium (CTAB) 0.6M.
Alla suddetta miscela viene quindi aggiunto H3PO4 in una concentrazione in peso, valutata rispetto al peso complessivo della miscela stessa, sostanzialmente pari al 85% fino al raggiungimento di un pH sostanzialmente pari a 3.9. H3PO4 is then added to the above mixture in a concentration by weight, evaluated with respect to the total weight of the mixture itself, substantially equal to 85% until a pH substantially equal to 3.9 is reached.
Il gel risultante viene riscaldato in un?autoclave di teflon a 65?C per due giorni in pressione autogena. The resulting gel is heated in a Teflon autoclave at 65°C for two days under autogenous pressure.
A questo punto, il prodotto ottenuto ? filtrato, lavato con etanolo, essiccato a 120?C e calcinato in muffola in condizioni statiche ad una temperatura compresa tra 400?C e 600?C. At this point, the product obtained? filtered, washed with ethanol, dried at 120°C and calcined in a muffle under static conditions at a temperature between 400°C and 600°C.
La velocit? di riscaldamento ? sostanzialmente pari a 10?C/min per una durata sostanzialmente compresa tra 3 e 6 ore. The speed? of heating ? substantially equal to 10?C/min for a duration substantially between 3 and 6 hours.
ESEMPIO PREPARATIVO 4: PREPARATION EXAMPLE 4:
Catalizzatore Ti/P/O - SINTESI PER IDROLISI E CONDENSAZIONE CON METODO SOL-GEL DEL PRECURSORE METALLICO ? Butossido (IV) di Titanio Catalyst Ti/P/O - SYNTHESIS BY HYDROLYSIS AND CONDENSATION WITH THE SOL-GEL METHOD OF THE METALLIC PRECURSOR ? Titanium (IV) butoxide
Il precursore metallico impiegato ? butossido (IV) di titanio. The metal precursor used? titanium butoxide (IV).
L?alcossido di titanio ? stato aggiunto goccia a goccia ad una soluzione acquosa di fosfato monobasico di ammonio (NH4)H2PO4 contenente nbutanolo. Titanium alkoxide? was added dropwise to an aqueous solution of dihydrogen ammonium phosphate (NH4)H2PO4 containing nbutanol.
Nel dettaglio, il rapporto molare tra butanolo/alcossido/(NH4)H2PO4/acqua ? di 1/0.125/0.0124/2. In detail, the molar ratio between butanol/alkoxide/(NH4)H2PO4/water ? of 1/0.125/0.0124/2.
Al termine dell?aggiunta il pH della soluzione viene portato ad un valore di 7 aggiungendo una soluzione acquosa di ammoniaca concentrata al 25%. A questo punto, il sistema ? mantenuto in agitazione per 24 ore a temperatura ambiente. At the end of the addition, the pH of the solution is brought to a value of 7 by adding a 25% concentrated ammonia aqueous solution. At this point, the system ? kept under stirring for 24 hours at room temperature.
Trascorse 24 ore, il solvente viene rimosso e le nanoparticelle vengono essiccate a 120?C durante la notte. After 24 hours, the solvent is removed and the nanoparticles are dried at 120°C overnight.
Successivamente, le nanoparticelle vengono calcinate a temperature tra 400?C e 600?C. Subsequently, the nanoparticles are calcined at temperatures between 400°C and 600°C.
La velocit? di riscaldamento ? sostanzialmente pari a 10?C/min per una durata sostanzialmente compresa tra 3 e 6 ore. The speed? of heating ? substantially equal to 10?C/min for a duration substantially between 3 and 6 hours.
ESEMPIO PREPARATIVO 5: PREPARATION EXAMPLE 5:
Catalizzatore Ti/P/O ? SINTESI PER IDROLISI E CONDENSAZIONE CON METODO SOL-GEL DEL PRECURSORE METALLICO ? Isopropossido (IV) di Titanio Ti/P/O catalyst ? SYNTHESIS OF THE METALLIC PRECURSOR BY HYDROLYSIS AND CONDENSATION WITH THE SOL-GEL METHOD ? Titanium isopropoxide (IV).
Il precursore metallico impiegato ? l?isopropossido (IV) di titanio. The metal precursor used? titanium isopropoxide (IV).
L?alcossido di titanio ? stato aggiunto goccia a goccia ad una soluzione acquosa di fosfato monobasico di ammonio (NH4)H2PO4 contenente una miscela 90:10 di etanolo e isopropanolo. Titanium alkoxide? was added dropwise to an aqueous solution of dihydrogen ammonium phosphate (NH4)H2PO4 containing a 90:10 mixture of ethanol and isopropanol.
Nel dettaglio, il rapporto molare tra etanolo|isopropanolo/alcossido/(NH4)H2PO4/acqua ? di 1/0.125/0.0124/2. In detail, the molar ratio between ethanol|isopropanol/alkoxide/(NH4)H2PO4/water ? of 1/0.125/0.0124/2.
Al termine dell?aggiunta, il pH della soluzione viene portato ad un valore di 7 aggiungendo una soluzione acquosa di ammoniaca concentrata al 25%. A questo punto, il sistema ? mantenuto in agitazione per 24 ore a temperatura ambiente. At the end of the addition, the pH of the solution is brought to a value of 7 by adding a 25% concentrated ammonia aqueous solution. At this point, the system ? kept under stirring for 24 hours at room temperature.
Trascorse 24 ore, il solvente viene rimosso e le nanoparticelle vengono essiccate a 120?C durante la notte. After 24 hours, the solvent is removed and the nanoparticles are dried at 120°C overnight.
Successivamente, le nanoparticelle vengono calcinate a temperature tra 400?C e 600?C. Subsequently, the nanoparticles are calcined at temperatures between 400°C and 600°C.
La velocit? di riscaldamento ? sostanzialmente pari a 10?C/min per una durata sostanzialmente compresa tra 3 e 6 ore. The speed? of heating ? substantially equal to 10?C/min for a duration substantially between 3 and 6 hours.
TEST EFFICIENZA CATALITICA CATALYTIC EFFICIENCY TEST
Qui di seguito si riporta un test allestito al fine di valutare l?efficienza catalitica dei fosfati metallici nella reazione di isomerizzazione dei glucidi, preferibilmente nella reazione di isomerizzazione di lattosio. A test set up in order to evaluate the catalytic efficiency of metal phosphates in the isomerization reaction of carbohydrates, preferably in the isomerization reaction of lactose, is reported below.
Le condizioni di reazione sono riportate qui di seguito: The reaction conditions are given below:
- V= 20 ml - V= 20ml
- Lattosio: 0.005 g/l in acqua; - Lactose: 0.005 g/l in water;
- mcat/mlat=1:1; - mcat/mlat=1:1;
- T= 200?C; - T= 200?C;
- t=3 ore; - t=3 hours;
- P autogena - P autogenous
TEST CORRELAZIONE TEMPERATURA DI REAZIONE ED EFFICIENZA CATALITICA TEST CORRELATION OF REACTION TEMPERATURE AND CATALYTIC EFFICIENCY
? stato allestito un test sperimentale al fine di valutare l?efficienza catalitica al variare della temperatura. Nel dettaglio, il suddetto test ? stato allestito impiegando il catalizzatore Nb/P/O su di un substrato di lattosio. Le condizioni di reazione sono riportate qui di seguito: ? an experimental test was set up in order to evaluate the catalytic efficiency as the temperature varies. In detail, the aforementioned test ? was prepared using the Nb/P/O catalyst on a lactose substrate. The reaction conditions are given below:
- V= 20ml - V= 20ml
- Lattosio: 0.005 g/l in acqua; - Lactose: 0.005 g/l in water;
- mcat/mlat=1:1; - mcat/mlat=1:1;
- T= 200?C; - T= 200?C;
- t=3 ore; - t=3 hours;
- P autogena; - P autogenous;
Dalla tabella soprariportata si evince che all?aumentare della temperatura aumenta anche la reattivit? e quindi la resa in idrossimetilfurfurale. From the above table it can be seen that as the temperature increases, the reactivity also increases. and then the yield in hydroxymethylfurfural.
Tuttavia, ? doveroso enfatizzare come al di sotto di 150?C non si verifica la scissione del lattosio nei suoi due componenti, glucosio e galattosio. However, ? it is necessary to emphasize that below 150°C the splitting of lactose into its two components, glucose and galactose, does not occur.
TEST CORRELAZIONE TEMPO DI REAZIONE ED EFFICIENZA TEST CORRELATION OF REACTION TIME AND EFFICIENCY
CATALITICA CATALYTIC
? stato allestito un test sperimentale al fine di valutare l?efficienza catalitica al variare del tempo di reazione. Nel dettaglio, il suddetto test ? stato allestito impiegando il catalizzatore Nb/P/O su di un substrato di lattosio. ? an experimental test was set up in order to evaluate the catalytic efficiency as the reaction time varied. In detail, the aforementioned test ? was prepared using the Nb/P/O catalyst on a lactose substrate.
Le condizioni di reazione sono riportate qui di seguito: The reaction conditions are given below:
- V= 20ml - V= 20ml
- Lattosio: 0.005 g/l in acqua; - Lactose: 0.005 g/l in water;
- mcat/mlat=1:1; - mcat/mlat=1:1;
- T= 150?C; - T= 150?C;
- P autogena; - P autogenous;
Dalla tabella soprariportata si osserva che il tempo di reazione di osserva che la resa in HMF ? direttamente proporzionale al tempo di reazione. From the above table it is observed that the reaction time of observes that the yield in HMF ? directly proportional to the reaction time.
TEST CORRELAZIONE VOLUME DI REAZIONE ED EFFICIENZA CATALITICA TEST CORRELATION OF REACTION VOLUME AND CATALYTIC EFFICIENCY
? stato allestito un test sperimentale al fine di valutare l?efficienza catalitica al variare del volume di reazione. Nel dettaglio, il suddetto test ? stato allestito impiegando il catalizzatore Nb/P/O su di un substrato di lattosio. ? an experimental test was set up in order to evaluate the catalytic efficiency as the reaction volume varies. In detail, the aforementioned test ? was prepared using the Nb/P/O catalyst on a lactose substrate.
Le condizioni di reazione sono riportate qui di seguito: The reaction conditions are given below:
- V= 50ml - V= 50ml
- Lattosio: 0.005 g/l in acqua; - Lactose: 0.005 g/l in water;
- mcat/mlat=1:1; - mcat/mlat=1:1;
- T= 150?C; - T= 150?C;
- P autogena; - P autogenous;
Dalla tabella soprariportata si evince che all?aumentare del volume di reazione la resa in HMF diminuisce. From the above table it can be seen that as the reaction volume increases, the yield of HMF decreases.
TEST CORRELAZIONE TIPOLOGIA DI SUBSTRATO ED EFFICIENZA CATALITICA CORRELATION TEST TYPE OF SUBSTRATE AND CATALYTIC EFFICIENCY
? stato allestito un test sperimentale al fine di valutare l?efficienza catalitica al variare del substrato. Nel dettaglio, il suddetto test ? stato allestito impiegando il catalizzatore Nb/P/O su di un substrato alternativamente scelto tra: lattosio, glucosio, galattosio, fruttosio, saccarosio. ? an experimental test was set up in order to evaluate the catalytic efficiency as the substrate varies. In detail, the aforementioned test ? was prepared using the Nb/P/O catalyst on a substrate alternatively selected from: lactose, glucose, galactose, fructose, sucrose.
Le condizioni di reazione sono riportate qui di seguito: The reaction conditions are given below:
- V= 50ml - V= 50ml
- Lattosio: 0.005 g/l in acqua; - Lactose: 0.005 g/l in water;
- mcat/mlat=1:1; - mcat/mlat=1:1;
- T= 150?C; - T= 150?C;
- P autogena; - P autogenous;
In un secondo aspetto, il presente trovato riguarda un catalizzatore per l?isomerizzazione di glucidi in idrossimetilfurfurale (HMF) comprendente almeno un fosfato metallico in cui il metallo ? scelto dall?elenco comprendente niobio, zirconio, afnio, titanio, alluminio. In a second aspect, the present invention relates to a catalyst for the isomerization of carbohydrates in hydroxymethylfurfural (HMF) comprising at least one metal phosphate in which the metal is chosen from the list including niobium, zirconium, hafnium, titanium, aluminium.
In un terzo aspetto, il presente trovato riguarda l?uso di un fosfato metallico comprendente uno tra niobio, zirconio, afnio, titanio, alluminio come catalizzatore per l?isomerizzazione di un glucide, in presenza di un solvente organico, per la preparazione di idrossimetilfurfurale (HMF). In a third aspect, the present invention relates to the use of a metal phosphate comprising one of niobium, zirconium, hafnium, titanium, aluminum as a catalyst for the isomerization of a glucide, in the presence of an organic solvent, for the preparation of hydroxymethylfurfural (HMF).
Si ? in pratica constatato come l?invenzione descritta raggiunga gli scopi proposti. Yup ? in practice it has been observed that the described invention achieves the proposed aim and objects.
In particolare, si sottolinea che il particolare accorgimento di prevedere l?impiego di un fosfato metallico in cui il metallo ? scelto tra niobio, zirconio, afnio, titanio, alluminio in combinazione con l?impiego di un substrato scelto dall?elenco comprendente glucosio, galattosio, fruttosio e saccarosio consente di ottenere idrossimetilfurfurale con una resa notevolmente superiore rispetto ai processi di tipo noto. In particular, it is emphasized that the particular expedient of providing for the use of a metal phosphate in which the metal is? selected from niobium, zirconium, hafnium, titanium, aluminum in combination with the use of a substrate selected from the list comprising glucose, galactose, fructose and sucrose allows to obtain hydroxymethylfurfural with a considerably higher yield than known processes.
Claims (14)
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CN106699703A (en) * | 2017-01-06 | 2017-05-24 | 吉林大学 | Method for preparing 5-hydroxymethylfurfural through catalyzing biomass sugar by zirconium phosphate-supported titanium dioxide |
WO2019000069A1 (en) * | 2017-06-29 | 2019-01-03 | The University Of Western Ontario | Bi-phasic continuous-flow tubular reactor and heterogeneous catalysts preparation method for production of 5-hydroxymethyl furfural |
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WO2014180979A1 (en) * | 2013-05-09 | 2014-11-13 | Novamont S.P.A. | Process for the synthesis of 5-hydroxymethylfurfural from saccharides |
CN106699703A (en) * | 2017-01-06 | 2017-05-24 | 吉林大学 | Method for preparing 5-hydroxymethylfurfural through catalyzing biomass sugar by zirconium phosphate-supported titanium dioxide |
WO2019000069A1 (en) * | 2017-06-29 | 2019-01-03 | The University Of Western Ontario | Bi-phasic continuous-flow tubular reactor and heterogeneous catalysts preparation method for production of 5-hydroxymethyl furfural |
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