CH651852A5 - PROCEDURE FOR THE PRODUCTION OF METHANOL MIXTURES AND SUPERIOR ALCOHOLS AND MIXTURES OBTAINED BY THAT PROCEDURE. - Google Patents
PROCEDURE FOR THE PRODUCTION OF METHANOL MIXTURES AND SUPERIOR ALCOHOLS AND MIXTURES OBTAINED BY THAT PROCEDURE. Download PDFInfo
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- CH651852A5 CH651852A5 CH5959/81A CH595981A CH651852A5 CH 651852 A5 CH651852 A5 CH 651852A5 CH 5959/81 A CH5959/81 A CH 5959/81A CH 595981 A CH595981 A CH 595981A CH 651852 A5 CH651852 A5 CH 651852A5
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
La presente invenzione riguarda un procedimento per la produzione di metanolo ed alcoli superiori e le miscele ottenute con detto procedimento. Le miscele in accordo con la presente invenzione in particolare, sono utili come sostitutive della benzina e possono essere anche ad essa miscelate in varie percen- 35 tuali per l'uso come carburanti di motori a combustione interna. Sono noti molti procedimenti per la produzione di metanolo in miscela con alcoli superiori. Essi tuttavia soffrono dell'inconveniente di dovere operare a pressioni alquanto elevate, generalmente comprese tra 17.000 a 35.000 KPa e questo costituì- 40 sce uno svantaggio considerevole sia per i costi di costruzione dell'impianto che ovviamente per i costi operativi. D'altra parte la necessità di lavorare ad alta pressione è ben nota dalla letteratura ad esempio Natta in «Catalysis», Vol. V. Reinhold Publishing Corp. New York, 1957, a pagina 136, dice chiara- 45 mente che a causa della notevole contrazione di volume che si ha in corrispondenza della produzione di alcoli superiori è necessario operare la sintesi ad alta pressione; ovviamente tanto più alcoli superiori si vogliono tanto più un aumento di pressione dovrebbe favorire la loro formazione. Le affermazioni di 50 Natta sono confermate dalla"tabella VII della relazione presentata da P.G. LAUX all'International Symposium on alcohol fuel tecnology, Wolfsburg, 21-23/11/1977 avente come titolo «The catalytic production and mechanism of formation of METHYL FUEL» dove la quantità di isobutanolo aumenta da 55 una percentuale dell'1,86% a 390°C e 179 bar ad una percentuale del 6,14% a 390°C e 308 bar. La tecnica nota mostra quindi chiaramente che la produzione di miscele di metanolo ed alcoli superiori è possibile solo operando a pressione elevata come insegna la termodinamica. • 60 The present invention relates to a process for the production of methanol and higher alcohols and the mixtures obtained with said process. The mixtures according to the present invention in particular are useful as a substitute for gasoline and can also be mixed with it in various percentages for use as fuels of internal combustion engines. Many processes are known for the production of methanol in a mixture with higher alcohols. However, they suffer from the drawback of having to operate at rather high pressures, generally between 17,000 and 35,000 KPa and this constituted a considerable disadvantage both for the construction costs of the plant and obviously for the operating costs. On the other hand, the need to work at high pressure is well known from literature, for example Natta in "Catalysis", Vol. V. Reinhold Publishing Corp. New York, 1957, on page 136, clearly says that because of the considerable contraction of volume that occurs in correspondence with the production of higher alcohols it is necessary to operate the synthesis at high pressure; obviously, the more higher alcohols are desired, the more pressure increases should favor their formation. 50 Natta's statements are confirmed by "Table VII of the report presented by PG LAUX to the International Symposium on alcohol fuel tecnology, Wolfsburg, 21-23 / 11/1977 entitled" The catalytic production and mechanism of formation of METHYL FUEL " where the quantity of isobutanol increases from 1.86% at 390 ° C and 179 bar from 6.14% at 390 ° C and 308 bar from 55. The prior art therefore clearly shows that the production of mixtures of methanol and higher alcohols is possible only by operating at high pressure as thermodynamics teaches. • 60
È stato ora sorprendentemente trovato che la produzione di miscele di metanolo ed alcoli superiori è possibile anche a pressione ridotta e che dette miscele hanno un contenuto di alcoli superiori notevolmente più elevato di quello che si ottiene alle alte pressioni utilizzate nella tecnica nota. Le miscele ottenute 65 assolvono meglio di quelle note il compito di solubilizzare l'acqua per il loro maggiore contenuto di alcoli superiori e esplicano la stessa funzióne di quelle note quando aggiunte alla benzina, il loro costo di produzione essendo d'altro canto notevolmente inferiore a causa delle ridotte condizioni di pressione alle quali sono ottenute. La ragione per la quale il metanolo non viene utilizzato da solo in miscela con la benzina e perciò vengono prodotte miscele di metanolo ed alcoli superiori e queste vengono addizionate alle benzine risiede nel fatto che nella benzina è sempre presente una certa quantità di acqua, derivante per lo più dall'acqua utilizzata per il lavaggio delle tubazioni nelle raffinerie e dall'umidità dell'aria. It has now been surprisingly found that the production of mixtures of methanol and higher alcohols is possible even at reduced pressure and that said mixtures have a considerably higher content of higher alcohols than that obtained at the high pressures used in the prior art. The mixtures obtained 65 perform better than the known ones the task of solubilizing the water due to their higher content of higher alcohols and perform the same function as those known when added to petrol, their production cost being on the other hand considerably lower than due to the reduced pressure conditions under which they are obtained. The reason why methanol is not used alone in a mixture with petrol and therefore mixtures of methanol and higher alcohols are produced and these are added to petrol is that a certain amount of water is always present in petrol, deriving from mostly from water used for washing pipes in refineries and from humidity in the air.
II metanolo quando è da solo si miscela con l'acqua presente nella benzina e si smiscela dalla benzina formando in tale modo nel serbatoio delle automobili due strati uno di benzina e l'altro inferiore di metanolo ed acqua. In queste condizioni i motori vengono a funzionare con grande difficoltà quando lo strato di metanolo ed acqua viene alimentato al posto della benzina. È noto che la presenza di alcoli superiori permette di solubilizzare il metanolo in presenza di acqua nelle benzine formandosi in tale modo miscele perfettamente omogenee. Le miscele in accordo con l'invenzione hanno un contenuto di alcoli superiori compreso tra il 25 e il 65% in peso e permettono la solubilizzazione del metanolo anche quando la concentrazione dell'acqua nelle benzine è elevatissima. Con le miscele della tecnica nota, generalmente al 10% in peso di alcoli superiori, è possibile tollerare, a —18°C, 1000 parti per milione in peso di acqua ad un rapporto alcoli-idrocarburi di 20/80. When it is alone, methanol mixes with the water present in petrol and mixes with petrol, thus forming two layers, one of petrol and the other of methanol and water, in the car tank. In these conditions the engines come into operation with great difficulty when the methanol and water layer is fed instead of petrol. It is known that the presence of higher alcohols allows the methanol to be solubilized in the presence of water in the gasolines, thus forming perfectly homogeneous mixtures. The mixtures according to the invention have a higher alcohol content of between 25 and 65% by weight and allow the solubilization of methanol even when the concentration of water in the gasoline is very high. With the prior art mixtures, generally at 10% by weight of higher alcohols, it is possible to tolerate, at -18 ° C, 1000 parts per million by weight of water at an alcohol / hydrocarbon ratio of 20/80.
Con lo stesso rapporto di 20/80 ed a —18°C le miscele secondo l'invenzione permettono di tollerare da un minimo di 2500 a più di 5000 parti per milione di acqua. Un oggetto della presente invenzione è un procedimento per la produzione di miscele di metanolo ed alcoli superiori contenenti dal 35 al 75% in peso di metanolo su base anidra consistente nell'alimentare una zona di reazione fornita di catalizzatore a base di zinco, cromo ed almeno un metallo alcalino con H2, CO ed eventualmente CO2 ed inerti con un rapporto H2/CO compreso tra 0,1 e 20, preferibilmente tra 0,5 e 5, a temperatura mantenuta nell'intervallo tra 300°C e 500°C, preferibilmente tra 350°C e 450°C ed una pressione compresa tra 2000 e 16000 KPa, preferibilmente tra 5000 e 13000 KPa. Il catalizzatore utilizzato in accordo con l'invenzione è costituito, come detto, da cromo e zinco ed almeno un metallo alcalino ed il rapporto in peso tra Zn e Cr presi come ossidi, è preferibilmente compreso tra 5/1 ed 1/1, il metallo alcalino essendo preferibilmente potassio e la quantità di metalli alcalini, presi come ossidi, è dallo 0,5 al 5% in peso del totale degli elementi presi come ossidi. La preparazione del catalizzatore può essere effettuata in maniere diverse. With the same ratio of 20/80 and at -18 ° C the mixtures according to the invention allow to tolerate from a minimum of 2500 to more than 5000 parts per million of water. An object of the present invention is a process for the production of mixtures of methanol and higher alcohols containing from 35 to 75% by weight of methanol on the anhydrous basis consisting of feeding a reaction zone equipped with a catalyst based on zinc, chromium and at least an alkaline metal with H2, CO and optionally CO2 and inert materials with an H2 / CO ratio between 0.1 and 20, preferably between 0.5 and 5, at a temperature maintained in the range between 300 ° C and 500 ° C, preferably between 350 ° C and 450 ° C and a pressure between 2000 and 16000 KPa, preferably between 5000 and 13000 KPa. The catalyst used in accordance with the invention consists, as said, of chromium and zinc and at least one alkaline metal and the weight ratio between Zn and Cr taken as oxides, is preferably between 5/1 and 1/1, the alkaline metal being preferably potassium and the quantity of alkaline metals, taken as oxides, is from 0.5 to 5% by weight of the total of the elements taken as oxides. The preparation of the catalyst can be carried out in different ways.
A titolo di esempio citiamo la precipitazione con NH3 dalle soluzioni dei nitrati di cromo e zinco o l'attacco con acido cromico di sospensioni acquose di ossido di zinco. Il catalizzatore può essere essiccato in stufa o per atomizzazione e sottoposto a successiva calcinazione. Il catalizzatore può essere estruso, pastigliato o in granuli di differente pezzatura e forma a seconda delle caratteristiche del reattore in cui deve essere utilizzato, regolandole opportunamente la porosità. As an example we mention the precipitation with NH3 from the solutions of chromium and zinc nitrates or the attack with chromic acid of aqueous suspensions of zinc oxide. The catalyst can be dried in a stove or by atomization and subjected to subsequent calcination. The catalyst can be extruded, pelleted or in granules of different size and shape according to the characteristics of the reactor in which it is to be used, by suitably adjusting the porosity.
I metalli alcalini sono introdotti per impregnazione del catalizzatore Zn-Cr già formato con soluzioni acquose di idrossido, carbonato, acetato, formiate od altro sale organico. Alternativamente il catalizzatore può essere preparato facendo reagire l'ossido di zinco con miscele di bicromati di ammonio e di metalli alcalini in rapporto tale che il catalizzatore finale contenga la quantità voluta di ossidi alcalini. Alkali metals are introduced by impregnation of the Zn-Cr catalyst already formed with aqueous solutions of hydroxide, carbonate, acetate, formates or other organic salt. Alternatively, the catalyst can be prepared by reacting the zinc oxide with mixtures of ammonium bicromates and alkaline metals in such a ratio that the final catalyst contains the desired amount of alkaline oxides.
Particolare attenzione deve essere dedicata alla riduzione del catalizzatore che è effettuata prima o dopo l'introduzione dei metalli alcalini diluendo il gas riducente che è preferibilmente idrogeno, con un gas inerte, quale ad esempio azoto e controllando la temperatura nel letto catalitico in modo che non superi i 350°C. Particular attention must be paid to the reduction of the catalyst which is carried out before or after the introduction of the alkali metals by diluting the reducing gas which is preferably hydrogen, with an inert gas, such as nitrogen for example, and controlling the temperature in the catalytic bed so that it does not exceed 350 ° C.
Un secondo oggetto della presente invenzione è costituito dalle miscele di metanolo ed alcoli superiori. Le miscele in ac A second object of the present invention consists of the mixtures of methanol and higher alcohols. Mixtures in ac
3 3
651 852 651 852
cordo con l'invenzione hanno un contenuto di metanolo che varia dal 35 al 75% in peso, un contenuto di etanolo dal 2 al 5% in peso, un contenuto di n. propanolo dal 3 al 12% in peso, un contenuto di isobutanolo dal 10 al 30% in peso, il resto, costituito da altri alcoli superiori con 5 o più atomi di carbonio, avendo una percentuale dal 5 al 25% in peso. According to the invention, they have a methanol content ranging from 35 to 75% by weight, an ethanol content from 2 to 5% by weight, a content of n. propanol from 3 to 12% by weight, an isobutanol content from 10 to 30% by weight, the rest consisting of other higher alcohols with 5 or more carbon atoms, having a percentage from 5 to 25% by weight.
Tutte le percentuali sopra riportate sono calcolate su base anidra, cioè trascurando l'acqua presente, prodotta in reazione, come sottoprodotto. C'è da osservare, riguardo agli intervalli di concentrazione sopra riportati, che i valori inferiori di concentrazione degli alcoli superiori e corrispondentemente il valore superiore di concentrazione del metanolo si hanno alla pressione più elevata dell'intervallo di pressione utilizzato in accordo con l'invenzione. Di conseguenza i valori superiori di concentrazione degli alcoli superiori ed il valore inferiore di concentrazione del metanolo si ottengono alle pressioni più basse. All the above percentages are calculated on an anhydrous basis, that is, by neglecting the water present, produced in reaction, as a by-product. It should be noted, with regard to the above concentration ranges, that the lower concentration values of the higher alcohols and correspondingly the higher concentration value of the methanol occur at the higher pressure of the pressure range used in accordance with the invention . Consequently, the higher concentration values of the higher alcohols and the lower concentration value of the methanol are obtained at the lowest pressures.
Riportiamo ora alcuni esempi aventi lo scopo di meglio illustrare l'invenzione, essendo inteso che la stessa non è da considerarsi da essi o ad essi limitata. Here are some examples whose purpose is to better illustrate the invention, since it is understood that the same is not to be considered by them or limited to them.
Esempio 1 Example 1
242,5 g di anidride cromica vengono disciolti in acqua distillata in modo da ottenere una soluzione al 30% in peso. Separatamente si prepara una sospensione acquosa di 736 g di ossido di zinco in due litri di acqua distillata che viene mantenuta sotto energica agitazione. Si aggiunge, sempre sotto agitazione, la soluzione di anidride cromica alla sospensione di ossido di zinco e si lascia sotto agitazione per parecchie ore in modo da ottenere una compietà omogeneizzazione. 242.5 g of chromic anhydride are dissolved in distilled water so as to obtain a 30% by weight solution. Separately, an aqueous suspension of 736 g of zinc oxide is prepared in two liters of distilled water which is kept under vigorous stirring. The chromic anhydride solution is added under stirring to the zinc oxide suspension and is left under stirring for several hours in order to obtain complete homogenization.
Si filtra il cromato basico di zinco, si secca mediante atomizzazione e si mescola la polvere secca con un legante costituito da stearato di zinco e si pastiglia. Le pastiglie, del diametro di 6 mm, vengono impregnate con una soluzione acquosa di acetato di potassio in quantità tale che sul catalizzatore finito e ridotto il contenuto in peso di K2O risulti intorno al 2,5%. DoTABELLA 1 The basic zinc chromate is filtered, dried by atomization and the dry powder is mixed with a binder consisting of zinc stearate and pasted. The tablets, with a diameter of 6 mm, are impregnated with an aqueous solution of potassium acetate in such an amount that on the finished and reduced catalyst the weight content of K2O is around 2.5%. DoTABELLA 1
Pressione KPa Pressure KPa
5000 5000
7000 7000
9000 . 9000.
13000 13000
Temperatura °C Temperature ° C
409-415 409-415
410-422 410-422
400-415 400-415
390-410 390-410
GHSV h~' GHSV h ~ '
5550 5550
11700 11700
14400 14400
14400 14400
Metanolo peso % Methanol weight%
43,0 43.0
46,3 46.3
57,2 57.2
68,8 68.8
Etanolo » Ethanol »
3,7 3.7
3,9 3.9
3,4 3.4
2,9 2.9
n Propanolo » n Propanol »
9,1 9.1
9,7 9.7
8,2 8.2
6,5 6.5
i Butanolo » the Butanol »
23,2 23.2
22,4 22.4
17,4 17.4
12,1 12.1
— altri alcoli superiori peso % - other higher alcohols weight%
21,0 21.0
17,7 17.7
13,8 13.8
9,7 9.7
con 5 o più atomi di carbonio with 5 or more carbon atoms
GHSV = velocità spaziale oraria del gas GHSV = hourly space velocity of the gas
•— con il termine alcoli superiori nell'esempio e nel testo si intendono anche piccole quantità di altri composti ossigenati che, ai fini degli usi come combustibile per motori a combustione interna, si comprano come gli alcoli. • - the term higher alcohols in the example and in the text also means small quantities of other oxygenated compounds which, for the purposes of uses as fuel for internal combustion engines, are bought as alcohols.
60 II contenuto totale di alcoli C2+presenti nel liquido accanto al metanolo risulta pari al 57% a 5.000 KPa, al 53,7% a 7.000 KPa, a 42,8% a 9.000 KPa ed al 31,2% a 13.000 KPa. 60 The total content of C2 + alcohols present in the liquid next to methanol is equal to 57% at 5,000 KPa, 53.7% at 7,000 KPa, 42.8% at 9,000 KPa and 31.2% at 13,000 KPa.
po avere essiccato per eliminare l'acqua di impregnazione il catalizzatore è pronto per la riduzione che viene eseguita nella stessa apparecchiatura in cui si esegue la reazione di sintesi. After having dried to eliminate the impregnation water, the catalyst is ready for the reduction which is carried out in the same apparatus in which the synthesis reaction is carried out.
100 cm3 di pastiglie vengono introdotte in un reattore tubo-5 lare in acciaio inossidabile immerso in un bagno a sabbia flui-dizzata e riscaldate fino a circa 300°C in corrente di azoto contenente circa il 2% di idrogeno, facendo attenzione che durante la riduzione la temperatura non superi i 350°C. La riduzione richiede un tempo relativamente lungo, circa 24 ore. Una volta 10 ridotto, il catalizzatore non deve più essere esposto all'aria. L'analisi chimica di un campione di tale catalizzatore ridotto fornisce i seguenti risultati: Zn O = 77,3%; Q2O3 = 19,0%; K2O = 2,4%; perdita alla calcinazione a 400°C = 1,3%; (le percentuali sono in peso). L'area superficiale risulta 125 m2/g. 15 II catalizzatore così ottenuto viene utilizzato per la preparazione di una miscela di metanolo ed alcoli superiori come viene illustrato nell'esempio seguente: 100 cm3 of tablets are introduced into a 5-tube stainless steel reactor immersed in a fluoridated sand bath and heated up to about 300 ° C in a nitrogen stream containing about 2% hydrogen, making sure that during the reduction the temperature does not exceed 350 ° C. The reduction takes a relatively long time, about 24 hours. Once reduced, the catalyst no longer needs to be exposed to air. Chemical analysis of a sample of this reduced catalyst provides the following results: Zn O = 77.3%; Q2O3 = 19.0%; K2O = 2.4%; loss on calcination at 400 ° C = 1.3%; (percentages are by weight). The surface area is 125 m2 / g. 15 The catalyst thus obtained is used for the preparation of a mixture of methanol and higher alcohols as illustrated in the following example:
Esempio 2 Example 2
20 Nel reattore descritto nell'esempio 1 contenente 100 cm3 del catalizzatore preparato come indicato in tale esempio viene alimentato un gas di sintesi avente la seguente composizione molare: 20 In the reactor described in Example 1 containing 100 cm3 of the catalyst prepared as indicated in this example, a synthesis gas having the following molar composition is fed:
25 25
H2 = 69',0% H2 = 69 ', 0%
CO = 30,5% CO = 30.5%
co2 = 0,1% co2 = 0.1%
CH4 = 0,1% CH4 = 0.1%
N2 = 0,3% N2 = 0.3%
30 La temperatura del letto catalitico viene mantenuta fra 390 e 420°C. Vengono effettuate 4 prove a 5.000, 7.000, 9.000 e 13.000 KPa. In ognuna delle prove il prodotto liquido di reazione viene separato dai gas mediante raffreddamento e condensazione. Le analisi dei campioni medi raccolti dopo 24 ore 35 di prova vennero eseguite mediante gascromatografia sul prodotto anidro ed hanno fornito i risultati riportati in tabella 1. 30 The temperature of the catalytic bed is maintained between 390 and 420 ° C. 4 tests are carried out at 5,000, 7,000, 9,000 and 13,000 KPa. In each of the tests, the liquid reaction product is separated from the gases by cooling and condensation. The analyzes of the average samples collected after 24 hours 35 of test were performed by gas chromatography on the anhydrous product and provided the results reported in table 1.
v v
Claims (6)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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IT24659/80A IT1193555B (en) | 1980-09-15 | 1980-09-15 | PROCEDURE FOR THE PRODUCTION OF METHANOL MIXTURES AND HIGHER ALCOHOLS AND MIXTURES OBTAINED BY THAT PROCEDURE |
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CH651852A5 true CH651852A5 (en) | 1985-10-15 |
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CH5959/81A CH651852A5 (en) | 1980-09-15 | 1981-09-15 | PROCEDURE FOR THE PRODUCTION OF METHANOL MIXTURES AND SUPERIOR ALCOHOLS AND MIXTURES OBTAINED BY THAT PROCEDURE. |
Country Status (32)
Country | Link |
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JP (1) | JPS5780486A (en) |
KR (1) | KR860000422B1 (en) |
AT (1) | AT375062B (en) |
AU (1) | AU546859B2 (en) |
BE (1) | BE890341A (en) |
BR (1) | BR8105777A (en) |
CA (1) | CA1187109A (en) |
CH (1) | CH651852A5 (en) |
CS (1) | CS221987B2 (en) |
CU (1) | CU35516A (en) |
DD (1) | DD201671A5 (en) |
DE (1) | DE3136088C2 (en) |
DK (1) | DK396981A (en) |
ES (1) | ES506040A0 (en) |
FI (1) | FI812866L (en) |
FR (1) | FR2490215B1 (en) |
GB (1) | GB2083469B (en) |
GR (1) | GR74675B (en) |
IE (1) | IE51556B1 (en) |
IN (1) | IN154478B (en) |
IT (1) | IT1193555B (en) |
LU (1) | LU83631A1 (en) |
NL (1) | NL8104257A (en) |
NO (1) | NO156007C (en) |
NZ (1) | NZ198082A (en) |
PH (1) | PH17030A (en) |
PL (1) | PL136284B1 (en) |
RO (1) | RO83096B (en) |
SE (1) | SE8105470L (en) |
TR (1) | TR22083A (en) |
YU (1) | YU202481A (en) |
ZA (1) | ZA816258B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3524317A1 (en) * | 1985-07-08 | 1987-01-15 | Union Rheinische Braunkohlen | METHOD FOR THE CATALYTIC PRODUCTION OF AN ALCOHOL MIXTURE WITH INCREASED ISOBUTANOL CONTENT |
US4705532A (en) * | 1985-07-15 | 1987-11-10 | The Standard Oil Company | Alcohol compositions for blending with gasoline |
IT1276931B1 (en) * | 1995-10-13 | 1997-11-03 | Snam Progetti | PROCEDURE FOR PRODUCING MIXTURES OF METHANOL AND HIGHER ALCOHOLS |
CN101918518A (en) * | 2008-01-04 | 2010-12-15 | 南加州大学 | Environmentally friendly ternary transportation flex-fuel of gasoline, methanol and bioethanol |
CN106390978B (en) * | 2016-09-14 | 2019-04-09 | 中国科学院大连化学物理研究所 | A kind of high temperature resistant synthesizing methanol by hydrogenating carbon dioxide catalyst and its preparation and application |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB275345A (en) * | 1926-05-12 | 1927-08-11 | Synthetic Ammonia & Nitrates | Improvements in or relating to the production of methanol and other oxygenated organic compounds |
GB323240A (en) * | 1928-06-22 | 1929-12-23 | Du Pont | Improvements in and relating to the catalytic synthesis of aliphatic alcohols |
DE868146C (en) * | 1944-01-04 | 1953-02-23 | Basf Ag | Process for the production of catalysts from chromium oxide and excess zinc oxide for the synthesis of alcohols from carbon oxide-hydrogen mixtures |
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1980
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1981
- 1981-08-18 NZ NZ198082A patent/NZ198082A/en unknown
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- 1981-08-22 IN IN937/CAL/81A patent/IN154478B/en unknown
- 1981-09-02 GB GB8126626A patent/GB2083469B/en not_active Expired
- 1981-09-08 DK DK396981A patent/DK396981A/en not_active Application Discontinuation
- 1981-09-08 PH PH26165A patent/PH17030A/en unknown
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- 1981-09-08 RO RO105256A patent/RO83096B/en unknown
- 1981-09-08 KR KR1019810003346A patent/KR860000422B1/en active
- 1981-09-08 BR BR8105777A patent/BR8105777A/en unknown
- 1981-09-09 ZA ZA816258A patent/ZA816258B/en unknown
- 1981-09-10 JP JP56142537A patent/JPS5780486A/en active Pending
- 1981-09-11 LU LU83631A patent/LU83631A1/en unknown
- 1981-09-11 DE DE3136088A patent/DE3136088C2/en not_active Expired
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- 1981-09-14 CA CA000385829A patent/CA1187109A/en not_active Expired
- 1981-09-14 FR FR8117329A patent/FR2490215B1/en not_active Expired
- 1981-09-14 CU CU8135516A patent/CU35516A/en unknown
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- 1981-09-14 BE BE0/205955A patent/BE890341A/en not_active IP Right Cessation
- 1981-09-15 CS CS816795A patent/CS221987B2/en unknown
- 1981-09-15 DD DD81233313A patent/DD201671A5/en unknown
- 1981-09-15 FI FI812866A patent/FI812866L/en not_active Application Discontinuation
- 1981-09-15 ES ES506040A patent/ES506040A0/en active Granted
- 1981-09-15 NL NL8104257A patent/NL8104257A/en not_active Application Discontinuation
- 1981-09-15 PL PL1981233029A patent/PL136284B1/en unknown
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