CA1187109A - Process for producing mixtures of methanol and higher alcohols and mixtures obtained thereby - Google Patents
Process for producing mixtures of methanol and higher alcohols and mixtures obtained therebyInfo
- Publication number
- CA1187109A CA1187109A CA000385829A CA385829A CA1187109A CA 1187109 A CA1187109 A CA 1187109A CA 000385829 A CA000385829 A CA 000385829A CA 385829 A CA385829 A CA 385829A CA 1187109 A CA1187109 A CA 1187109A
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- Prior art keywords
- mixtures
- methanol
- weight
- higher alcohols
- kpa
- Prior art date
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Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
PROCESS FOR PRODUCING MIXTURES OF METHANOL AND
HIGHER ALCOHOLS AND MIXTURES OBTAINED THEREBY.
A B S T R A C T
Process for the production of mixtures of methanol and higher alcohols to be used, more particularly, alone or in admixture with gasoline, as fuels, compris-ing the steps of reacting H2 and CO, possibly in the presence of CO2, with a molar ratio H2:CO comprised between 0.1 and 20, preferably between 0.5 and 5, at a temperature from 300°C to 500°C, preferably from 350°C
to 450°C and under a pressure from 2000 to 16000 KPa, in the presence of a catalyst based on chromium, zinc and at least one alkali metal, wherein the weight ratio of Zn to Cr, considered as oxides, is comprised between 5:1 and 1:1 and the alkali metals or the alkali metals as oxides are in an amount equal to 0.5%-5% by wt relative to the total of the elements considered as oxides.
HIGHER ALCOHOLS AND MIXTURES OBTAINED THEREBY.
A B S T R A C T
Process for the production of mixtures of methanol and higher alcohols to be used, more particularly, alone or in admixture with gasoline, as fuels, compris-ing the steps of reacting H2 and CO, possibly in the presence of CO2, with a molar ratio H2:CO comprised between 0.1 and 20, preferably between 0.5 and 5, at a temperature from 300°C to 500°C, preferably from 350°C
to 450°C and under a pressure from 2000 to 16000 KPa, in the presence of a catalyst based on chromium, zinc and at least one alkali metal, wherein the weight ratio of Zn to Cr, considered as oxides, is comprised between 5:1 and 1:1 and the alkali metals or the alkali metals as oxides are in an amount equal to 0.5%-5% by wt relative to the total of the elements considered as oxides.
Description
~L~8~
C~SE_1 3 3 3 PROCESS FOR PRODUCING ~IIXTURE~ OF PIETHANOL AND HIGHEK
ALCOHOLS A~D ~IIXTURES OBTAINED THEREBY.
This in~ention relatcs to a process Eor the produo~-ion of methanol and higher alcohols and the mixtures ob-tained with that process. The mixtures according to the pres~nt inventîon, ~ore particularly, are useful as sub~
5 stitutes o~ ga.soline and can also be admixed therewith in ~arious percentages for us~ as fuels in internal cnm-bustion eng.,ne~; ., ~ any p;rocesses are known for produeing methanol in ~dmixture w~ h higher alcohols. They, howaver, suffer 10 from the shortcoming of requirin~ comparatively hi~h work ing pre~sures, whlch are gen~rall~ eolllprised bet~Yeen 17~000 and 35,000 KPa and thi.s is a considerable defec~
both ~rom the poin~ of view of -~he fi.rst cost and ~he running CGStS~ as i.t is obvious~ On the other hand, the 15 require~en~ of working under hi~h pressures is well k~o~vn from ~ihe li.terature and, for example, Natt~ in t~Catsiysi.6lt, Vol,Y, Reinhold ~ublishi.ng Corp,i~iew Yor~ (1957), on pap~e 1363 elearly s~ates~that~ due to the consi.dera~le Yolume raduction ~Ihich trllces ~lace when producins higher alcohols~
the synthes}s must ~)e effec~ed undcr high pressure;~: ob-'~
~iously th~ more higher alcoho1.s are requested, themore an increase o pressure should encourage their formation The statements by Natta ar~ corroborated. by Table ~II of the paper presented by P.G~Laux at the International Symposium on alcohol ~uel technolo~y, Wolf~burg, 21 to 23 ~ovember, 1977, having the title:
17The catalytic production and mechanism of formatio~ of methyl fuel", where the amount of ifiobutanol is increas-ed from a perc~ntage of 1.S6% at 390~C and 176 kg/cm , to a percentage of 6.14% at 390C and 302 kg/cm G
The conventional a.rt thus clearly shows that the pro~
duction of mix~ures of methanol and hi.gher alcohols is possible only when working under high pressures~ ~ccord~
in~ to th~ teachings of thermodynamics.
I~ has now surprisin~ly been found that the product-ion of mixtures of methanol and higher alcohols can be carried out also under reduccd pressures and that such mixtures have a content of higher alcohols whjch is corl-siderably lligher than that which is obtained usder the high pressurefi u~ed by the known art. The mixtures thu3 obta~ned fulfil, better than the known ~ixtures, the t~s~. of solu-~ilizing water due to their hl~h~r content of higher al-cohols and act in the same way as the kno~n ~ ures whe added to the ga~oline, while their yroduction cost is con~
~5 siderably lower due to the condi.tions of reduced pre3sures under which ~hey are prof1uced. The rea~on why methanol is ~evsr u~ed ~lone in admlxture ~i.th ga.~oline and thus mlxt~
ure6 o~ ~etha~o1 and hi~her- alcollol.s are procluced to be ~I!L 9L8~7~
added to gasolines, lies in the fact that a certain amount of water is always present in gasoline, said water deriving most usually from the water used for washiny the pipings in the refineries, or from the moisture in the air. Methanolt when used alone, is admixed with the water which is present in the gasoline and is split from gasoline, so that in the tanks of the cars two layers are formed, viz. one of gasoline and the other of methanol and water. Under these circumstan-ces, the engines run with great difficulties when the layer of methanol and water is dispensed instead of gasoline.
It is known that the presence of higher alcohols permits to solubilize methanol when water i5 present in gasoline, because thoroughly homogeneous mixtures are thus formed. The mixtures according to the invention have a content of higher alcohols comprised between 25~ and 65%
by wt and permit that methanol may be solubilized even i~
the water content of gasolines is extremely high.
With the mixtures of the prior art, which generally contain 10% of higher alcohols by wt, it is possible to tolerate, at -18C, lO00 parts per ~illion (ppm) of water with a ratio alcohols/hycrocarbons of 20:80. With the same ratio of 20:80 and at -18C, the mixtures according to the invention permit that from a minimum of 2,500 ppm to more than 5,000 ppm of water may be tolerated.
The present invention provides a process for the production of mixtures of methanol and higher alcohols, to be used, more particularly, as gasoline substitutes or in admixtures therewith as fuels for internal combustion engines, comprising the step of reacting H2 and CO, possibly in the presence of CO2 and inert gases with a molax ratio H2:CO
ranging from 0.1 to 20, and at a temperature from 300C to 500C, characterized in that said mixtures are obtained under a pressure selected from 2,000 KPa and 16,000 KPa and with a catalyst based on chromium, zinc and at least one alkali metal.
,, " "~, ~
~ d ;
In accordance with the process of the present invention mixtures of methanol and higher alcohols, may be produced containin~ from 35% to 75% by wt of methanol on an anhydrous base, the process, as indicated above comprising the step of feeding to a reaction zone containing a catalyst based on chromium, zinc and at least one alkali metal, hydro-gen and carbon monoxide and possibly CO2 and inerts with a ratio H2:CO comprised between 0.1 and 2Q, preferably between ~.5 and 5, at a temperature maintained in the range between 300C and 500C, preferably between 350C and 450C and under a pressure comprised between 2000 and 16000 KPa, preferably between 5000 and 13000 KPa.
The catalyst used according to the invention is composed, as outlined above, of chromium and zinc and at least one alkali metal and the ratio of Zn to Cr by wt, considered as oxides, is preferably comprised between 5:1 and 1:1, the alkali metal being preferably potassium and the amount of alkali metals, considered as oxides, is from 0.5% to 5% by wt relative to the total wt of the elements considered as oxides.
The preparation of the catalyst may be effected i~ a number of ways.
By way of example, there can be mentioned the precipitation with NH3 from the solutions of nitrates of chromium and zinc, or the attack with chromic acid of a~ueous suspensions of zinc oxide. The catalyst can be dried in an oven or by atomization and then subjected to firing.
The catalyst can be extruded, pelletized or granulated in different sizes and shapes consistently with the charac-teristics of the reactor in which it must be used, itsporosity being appropriately regulated.
~' The alkali ~le-tals are introduced by impre~rnat ing an already for~led Zn-Cr catalys~ wit}l a~ueous so-lutiorls of hyd.roxi~e, carbonate~ acetate, ~-ormate and other organlc salts. As an al~ernative, the catalys~ can be prepared by reac~ing~ zinc oxide with mixtures of bi-chromates of ammonium and of alkali metals in such a ra-tio that the final catal~st contains the ~e.sired quantity of alkali metal oxides Special care should be taken in the re~uction of the ca~alyst, rhicll is carried out before or after the in-troduction o- th~ alkal.i metals, by di.luting the re-duc~-ing gas, wllich is preferably hydro~en9 witll an inert ga., such as ni.trQgen, and controll.ing the tempera~l1re of the catalytic l~ed so that it never exceeds 350C.
~nother object o~ the prescnt invèntion is to provide mi.xtures of methanol and hig-he1 alcohols.
The mi.xtures according to the invention have a me--t.hanol contcnt whicll varies from 35% to 75% by w-L~ a con-tent of etllanol from 2% to 5~0 by w-t, a conten-t of nor.pro-panol frolll 3~ to 12% by w~, a content of isobu~ano1. from10% to 307~ by wt, the balance be:ing co~lposed of other higher alcohols having more tharL 5 car~on atoms an~ bein~
frol~ 5~ to 25% by wt.
All the percentages are calcul~ed on an anh-ydrous base, tllat is neglecting the watol wh:i.cll i~ presel-t be-eallsc it has heeil produced ~.n t}le reaction as a by prodl1ct It shoul~l he observed, :in connect:ion with the concon---trat;iol-J ranges reporl:od above J ~:hat thc lo~-Jer vcl1.ues or ~7 6.
the concent~ation Eor the hi~h~r alcohols, and, co~-respondin~ly, the higher values of concent~at;ion ~or me~}lanol are e~perienced with the hi.gher pr~essure or the pressule range use~ accordin~r to the i.nvention.
Conseqllently~ the top ~alues of conccntrat;ion for the higher alcohols and t;he lowermost values of thc con--centrati.ons of methanol are obtained with the lower pre~-sure of the range.
A few examples will now be reported in order better to illustrate t;he in~ention; it being unr1erstood that the invention shall not ~e con~trued as being limited ther~by vr ~hereto.
EXA~IPIE
242.5 g of chromiur,l trioxide are dissol~-ed in dj.st.
water so as to obtain a solution having a conceI1tration o~ 30~ by wt;- An aqueous slurry of 736 g of zinc o~.ide in two lit3rs of diSt. water is separately prepared and ifi kept under vi.gorous stir~ing. The solut;icn of chro~ m triox:ide is ad~ed, wiJ~Il stirring, to the zinc oxide slurry and ~tirrin~ :Ls continued during r.lany houI~s so a~ t;o achie-ve a oomplet~ hoinogeneiYation. T}Ie basic zinc chroma~e is collected on a filter and the dIy powder is admixed ~ith a binder composed of ~inc stearate ~nd the mixture is pelleti~edO The pell.ets, havin~ a diameter o~ 6 mm, arc
C~SE_1 3 3 3 PROCESS FOR PRODUCING ~IIXTURE~ OF PIETHANOL AND HIGHEK
ALCOHOLS A~D ~IIXTURES OBTAINED THEREBY.
This in~ention relatcs to a process Eor the produo~-ion of methanol and higher alcohols and the mixtures ob-tained with that process. The mixtures according to the pres~nt inventîon, ~ore particularly, are useful as sub~
5 stitutes o~ ga.soline and can also be admixed therewith in ~arious percentages for us~ as fuels in internal cnm-bustion eng.,ne~; ., ~ any p;rocesses are known for produeing methanol in ~dmixture w~ h higher alcohols. They, howaver, suffer 10 from the shortcoming of requirin~ comparatively hi~h work ing pre~sures, whlch are gen~rall~ eolllprised bet~Yeen 17~000 and 35,000 KPa and thi.s is a considerable defec~
both ~rom the poin~ of view of -~he fi.rst cost and ~he running CGStS~ as i.t is obvious~ On the other hand, the 15 require~en~ of working under hi~h pressures is well k~o~vn from ~ihe li.terature and, for example, Natt~ in t~Catsiysi.6lt, Vol,Y, Reinhold ~ublishi.ng Corp,i~iew Yor~ (1957), on pap~e 1363 elearly s~ates~that~ due to the consi.dera~le Yolume raduction ~Ihich trllces ~lace when producins higher alcohols~
the synthes}s must ~)e effec~ed undcr high pressure;~: ob-'~
~iously th~ more higher alcoho1.s are requested, themore an increase o pressure should encourage their formation The statements by Natta ar~ corroborated. by Table ~II of the paper presented by P.G~Laux at the International Symposium on alcohol ~uel technolo~y, Wolf~burg, 21 to 23 ~ovember, 1977, having the title:
17The catalytic production and mechanism of formatio~ of methyl fuel", where the amount of ifiobutanol is increas-ed from a perc~ntage of 1.S6% at 390~C and 176 kg/cm , to a percentage of 6.14% at 390C and 302 kg/cm G
The conventional a.rt thus clearly shows that the pro~
duction of mix~ures of methanol and hi.gher alcohols is possible only when working under high pressures~ ~ccord~
in~ to th~ teachings of thermodynamics.
I~ has now surprisin~ly been found that the product-ion of mixtures of methanol and higher alcohols can be carried out also under reduccd pressures and that such mixtures have a content of higher alcohols whjch is corl-siderably lligher than that which is obtained usder the high pressurefi u~ed by the known art. The mixtures thu3 obta~ned fulfil, better than the known ~ixtures, the t~s~. of solu-~ilizing water due to their hl~h~r content of higher al-cohols and act in the same way as the kno~n ~ ures whe added to the ga~oline, while their yroduction cost is con~
~5 siderably lower due to the condi.tions of reduced pre3sures under which ~hey are prof1uced. The rea~on why methanol is ~evsr u~ed ~lone in admlxture ~i.th ga.~oline and thus mlxt~
ure6 o~ ~etha~o1 and hi~her- alcollol.s are procluced to be ~I!L 9L8~7~
added to gasolines, lies in the fact that a certain amount of water is always present in gasoline, said water deriving most usually from the water used for washiny the pipings in the refineries, or from the moisture in the air. Methanolt when used alone, is admixed with the water which is present in the gasoline and is split from gasoline, so that in the tanks of the cars two layers are formed, viz. one of gasoline and the other of methanol and water. Under these circumstan-ces, the engines run with great difficulties when the layer of methanol and water is dispensed instead of gasoline.
It is known that the presence of higher alcohols permits to solubilize methanol when water i5 present in gasoline, because thoroughly homogeneous mixtures are thus formed. The mixtures according to the invention have a content of higher alcohols comprised between 25~ and 65%
by wt and permit that methanol may be solubilized even i~
the water content of gasolines is extremely high.
With the mixtures of the prior art, which generally contain 10% of higher alcohols by wt, it is possible to tolerate, at -18C, lO00 parts per ~illion (ppm) of water with a ratio alcohols/hycrocarbons of 20:80. With the same ratio of 20:80 and at -18C, the mixtures according to the invention permit that from a minimum of 2,500 ppm to more than 5,000 ppm of water may be tolerated.
The present invention provides a process for the production of mixtures of methanol and higher alcohols, to be used, more particularly, as gasoline substitutes or in admixtures therewith as fuels for internal combustion engines, comprising the step of reacting H2 and CO, possibly in the presence of CO2 and inert gases with a molax ratio H2:CO
ranging from 0.1 to 20, and at a temperature from 300C to 500C, characterized in that said mixtures are obtained under a pressure selected from 2,000 KPa and 16,000 KPa and with a catalyst based on chromium, zinc and at least one alkali metal.
,, " "~, ~
~ d ;
In accordance with the process of the present invention mixtures of methanol and higher alcohols, may be produced containin~ from 35% to 75% by wt of methanol on an anhydrous base, the process, as indicated above comprising the step of feeding to a reaction zone containing a catalyst based on chromium, zinc and at least one alkali metal, hydro-gen and carbon monoxide and possibly CO2 and inerts with a ratio H2:CO comprised between 0.1 and 2Q, preferably between ~.5 and 5, at a temperature maintained in the range between 300C and 500C, preferably between 350C and 450C and under a pressure comprised between 2000 and 16000 KPa, preferably between 5000 and 13000 KPa.
The catalyst used according to the invention is composed, as outlined above, of chromium and zinc and at least one alkali metal and the ratio of Zn to Cr by wt, considered as oxides, is preferably comprised between 5:1 and 1:1, the alkali metal being preferably potassium and the amount of alkali metals, considered as oxides, is from 0.5% to 5% by wt relative to the total wt of the elements considered as oxides.
The preparation of the catalyst may be effected i~ a number of ways.
By way of example, there can be mentioned the precipitation with NH3 from the solutions of nitrates of chromium and zinc, or the attack with chromic acid of a~ueous suspensions of zinc oxide. The catalyst can be dried in an oven or by atomization and then subjected to firing.
The catalyst can be extruded, pelletized or granulated in different sizes and shapes consistently with the charac-teristics of the reactor in which it must be used, itsporosity being appropriately regulated.
~' The alkali ~le-tals are introduced by impre~rnat ing an already for~led Zn-Cr catalys~ wit}l a~ueous so-lutiorls of hyd.roxi~e, carbonate~ acetate, ~-ormate and other organlc salts. As an al~ernative, the catalys~ can be prepared by reac~ing~ zinc oxide with mixtures of bi-chromates of ammonium and of alkali metals in such a ra-tio that the final catal~st contains the ~e.sired quantity of alkali metal oxides Special care should be taken in the re~uction of the ca~alyst, rhicll is carried out before or after the in-troduction o- th~ alkal.i metals, by di.luting the re-duc~-ing gas, wllich is preferably hydro~en9 witll an inert ga., such as ni.trQgen, and controll.ing the tempera~l1re of the catalytic l~ed so that it never exceeds 350C.
~nother object o~ the prescnt invèntion is to provide mi.xtures of methanol and hig-he1 alcohols.
The mi.xtures according to the invention have a me--t.hanol contcnt whicll varies from 35% to 75% by w-L~ a con-tent of etllanol from 2% to 5~0 by w-t, a conten-t of nor.pro-panol frolll 3~ to 12% by w~, a content of isobu~ano1. from10% to 307~ by wt, the balance be:ing co~lposed of other higher alcohols having more tharL 5 car~on atoms an~ bein~
frol~ 5~ to 25% by wt.
All the percentages are calcul~ed on an anh-ydrous base, tllat is neglecting the watol wh:i.cll i~ presel-t be-eallsc it has heeil produced ~.n t}le reaction as a by prodl1ct It shoul~l he observed, :in connect:ion with the concon---trat;iol-J ranges reporl:od above J ~:hat thc lo~-Jer vcl1.ues or ~7 6.
the concent~ation Eor the hi~h~r alcohols, and, co~-respondin~ly, the higher values of concent~at;ion ~or me~}lanol are e~perienced with the hi.gher pr~essure or the pressule range use~ accordin~r to the i.nvention.
Conseqllently~ the top ~alues of conccntrat;ion for the higher alcohols and t;he lowermost values of thc con--centrati.ons of methanol are obtained with the lower pre~-sure of the range.
A few examples will now be reported in order better to illustrate t;he in~ention; it being unr1erstood that the invention shall not ~e con~trued as being limited ther~by vr ~hereto.
EXA~IPIE
242.5 g of chromiur,l trioxide are dissol~-ed in dj.st.
water so as to obtain a solution having a conceI1tration o~ 30~ by wt;- An aqueous slurry of 736 g of zinc o~.ide in two lit3rs of diSt. water is separately prepared and ifi kept under vi.gorous stir~ing. The solut;icn of chro~ m triox:ide is ad~ed, wiJ~Il stirring, to the zinc oxide slurry and ~tirrin~ :Ls continued during r.lany houI~s so a~ t;o achie-ve a oomplet~ hoinogeneiYation. T}Ie basic zinc chroma~e is collected on a filter and the dIy powder is admixed ~ith a binder composed of ~inc stearate ~nd the mixture is pelleti~edO The pell.ets, havin~ a diameter o~ 6 mm, arc
2~ soaked by an aqueous olution oP potassium acetate in ~such an amoun~ that on the finished an~ ~educed ca~alyst the content of K20 by wt i.s abol~ 2.5~.
After drir.ing to lei~x~7;e the irIlpregrlatic)n wa~sl$ t]le catalys1; .is reatly for tlle reductiol~ to be ca:rri-3tl out il~ the same reactor in which the synt,hc~sis ,ril:l b~ e~
Pecte~l. 100 C~tl3 OIC pellets are introdv.ced in a sta:in-less stieel tubu].ar reactor :i~mnersed in a bat'l c>r î lU:i.d!i~
5 ~d sa-ld and h~3a-ved up t,o 300 C in a nitrogen stream con-taini.ng about 2~ of hydrogen~ care bein~, taken to that the -~er,~perature cluring the reduc~ion ne~er excce~s 350 C .
The reduct.ion requir~s a co~nparati~ely long tirneg about 2.~ ~ours . Oncs it has beerl reducesl ~ the catalyfi t shal:L
10 not b~ exposed to air any more. The chemical analysis ol.
such ~ r~3duce~ cataly~;t g:i ves the ~2ollotring result;s ZnO ~ ~1 ~% - Cr203 -- 2~ ~ 4% K2 loss at 400 C -- 1. 3% g a.ll thc p-ercenta~-es being ~y wt~
Th~ spec:iPic surface area i.s 125 tn /g, lS The cataly.st thu6 ob-taine~ is used or ~he prepara-~
ion of ~ethano1 and highe~ alcohols as sho~-l in the fo lo~ing example EXA~iPLE 2 .. ~
~ eactor descri.bed in ~xa~tlple 1 and cor.~,ain~
ing 100 cm of ~he ca~a1yst as prepared in ~aid ~example~
a syn~h~sis gas is in~rGcluced~ ~hic}l has the follo~ Ag composition~ on a molar b~sis -~ - 69.o~
C~ ~ 3~S%
25 ~2 - V.~%
C~l~ ~ 0.1%
N2 - 0.3%.
T~ .npe~ ut~ o* ~ S CLll;?~lyt.~ i.,5 Illa:~llt,~li.ncd bet~een 390C and 420C. ~our tests are carried ouk, under a pressure of 5~00() KPa~ 7,000 KPa, 9,00G KP~
and 13,000 ICPaQ respectively, In each test t}le :Liquid reaction yroduct is separated ro1ll tE1e gas by cooling and condensation. The analyses of the a~era~e samples collected af~er a 2~-hour tes~ have been made gascEIro-matographicall~ on the anhydro~s product and. ga~e the results tabu1.ated in tEIe following Table.
9. t,q td a Ul o rl ~
~ rt O ~ O
g ~ O c~
'` O '` CO C~ ~C`l C~
~v)CJ~ ~ ~ ~ J 4.
O
.~ ~J
~ ~ ~ C`~ ~ a~ r~ o t,q O I O ~ .~ ~ r~l O Ot~ c~ o~ 40 O O ~4~
~ O ~ O
Ct~ ~d' r~
h ~;
~ r ~ t~ ~ 1 r--I
O el~ O ~ 5 0 O I O ~ O~ t~ O
O O 1~ e~ C`l 7~1 ~j r~
h ~ ,.c O ~
~ ~ t~ ,Q
¢ ~.~ ~
0 rl rl r-l ti;
; 4 ~ ~ O
O d O O ~ ~I c~ o ~ I o O I O o S¦ rl r.~? ~ sl~ -~
rr) ~ ~ ~~ ~ ~3 ~ S~
r?~.? 0 ~3 C~C~ O
O
r~ r^l ;~ O
rl C) ~:
t i 1-l t~ ~ ~ S'~J ~ Q) O O O5) 0 -S7 r~ 5j ~c, 0 ~ In ~rl 0 ~ s. I Q~r?
U ~ ~ a V~3 t1 O P ~ O 5"~ r~ sa ru -r) Cs~ ~ O
Or-l h ~ ?;i Ul C~ '6'~ i 0 '` Q~ slj 51~ r -l C~r~ h Ul Q~
~ sa s~ ~D O ~ r~l 1-) i r~ Q~ ?~
t~ .~ 0r-~0 ~5 r~' ~a O ~ ~ ~q 5~ q H 5 ~ ~ d ,~d~ .~ s'~
~ ~ 5~ ~ rr 0 U~
0 1~ 0 ~a ~ ?,~
P~ ?~ ? ~.1'~ ~1 0 r~l 5!~
7~Q~
10 ~
The total content o~ C2-~ alcohols present in the liquid with methanol is 57% at 5,000 KPa, 53.7%
at 7,000 KPas 42.8% at 9,000 KPa and 31.2% at 13,000 KPa.
After drir.ing to lei~x~7;e the irIlpregrlatic)n wa~sl$ t]le catalys1; .is reatly for tlle reductiol~ to be ca:rri-3tl out il~ the same reactor in which the synt,hc~sis ,ril:l b~ e~
Pecte~l. 100 C~tl3 OIC pellets are introdv.ced in a sta:in-less stieel tubu].ar reactor :i~mnersed in a bat'l c>r î lU:i.d!i~
5 ~d sa-ld and h~3a-ved up t,o 300 C in a nitrogen stream con-taini.ng about 2~ of hydrogen~ care bein~, taken to that the -~er,~perature cluring the reduc~ion ne~er excce~s 350 C .
The reduct.ion requir~s a co~nparati~ely long tirneg about 2.~ ~ours . Oncs it has beerl reducesl ~ the catalyfi t shal:L
10 not b~ exposed to air any more. The chemical analysis ol.
such ~ r~3duce~ cataly~;t g:i ves the ~2ollotring result;s ZnO ~ ~1 ~% - Cr203 -- 2~ ~ 4% K2 loss at 400 C -- 1. 3% g a.ll thc p-ercenta~-es being ~y wt~
Th~ spec:iPic surface area i.s 125 tn /g, lS The cataly.st thu6 ob-taine~ is used or ~he prepara-~
ion of ~ethano1 and highe~ alcohols as sho~-l in the fo lo~ing example EXA~iPLE 2 .. ~
~ eactor descri.bed in ~xa~tlple 1 and cor.~,ain~
ing 100 cm of ~he ca~a1yst as prepared in ~aid ~example~
a syn~h~sis gas is in~rGcluced~ ~hic}l has the follo~ Ag composition~ on a molar b~sis -~ - 69.o~
C~ ~ 3~S%
25 ~2 - V.~%
C~l~ ~ 0.1%
N2 - 0.3%.
T~ .npe~ ut~ o* ~ S CLll;?~lyt.~ i.,5 Illa:~llt,~li.ncd bet~een 390C and 420C. ~our tests are carried ouk, under a pressure of 5~00() KPa~ 7,000 KPa, 9,00G KP~
and 13,000 ICPaQ respectively, In each test t}le :Liquid reaction yroduct is separated ro1ll tE1e gas by cooling and condensation. The analyses of the a~era~e samples collected af~er a 2~-hour tes~ have been made gascEIro-matographicall~ on the anhydro~s product and. ga~e the results tabu1.ated in tEIe following Table.
9. t,q td a Ul o rl ~
~ rt O ~ O
g ~ O c~
'` O '` CO C~ ~C`l C~
~v)CJ~ ~ ~ ~ J 4.
O
.~ ~J
~ ~ ~ C`~ ~ a~ r~ o t,q O I O ~ .~ ~ r~l O Ot~ c~ o~ 40 O O ~4~
~ O ~ O
Ct~ ~d' r~
h ~;
~ r ~ t~ ~ 1 r--I
O el~ O ~ 5 0 O I O ~ O~ t~ O
O O 1~ e~ C`l 7~1 ~j r~
h ~ ,.c O ~
~ ~ t~ ,Q
¢ ~.~ ~
0 rl rl r-l ti;
; 4 ~ ~ O
O d O O ~ ~I c~ o ~ I o O I O o S¦ rl r.~? ~ sl~ -~
rr) ~ ~ ~~ ~ ~3 ~ S~
r?~.? 0 ~3 C~C~ O
O
r~ r^l ;~ O
rl C) ~:
t i 1-l t~ ~ ~ S'~J ~ Q) O O O5) 0 -S7 r~ 5j ~c, 0 ~ In ~rl 0 ~ s. I Q~r?
U ~ ~ a V~3 t1 O P ~ O 5"~ r~ sa ru -r) Cs~ ~ O
Or-l h ~ ?;i Ul C~ '6'~ i 0 '` Q~ slj 51~ r -l C~r~ h Ul Q~
~ sa s~ ~D O ~ r~l 1-) i r~ Q~ ?~
t~ .~ 0r-~0 ~5 r~' ~a O ~ ~ ~q 5~ q H 5 ~ ~ d ,~d~ .~ s'~
~ ~ 5~ ~ rr 0 U~
0 1~ 0 ~a ~ ?,~
P~ ?~ ? ~.1'~ ~1 0 r~l 5!~
7~Q~
10 ~
The total content o~ C2-~ alcohols present in the liquid with methanol is 57% at 5,000 KPa, 53.7%
at 7,000 KPas 42.8% at 9,000 KPa and 31.2% at 13,000 KPa.
Claims (9)
1. A process for the production of mixtures of methanol and higher alcohols, to be used, more particularly, as gasoline substitutes or in admixtures therewith as fuels for internal combustion engines, comprising the step of reacting H2 and CO, possibly in the presence of CO2 and inert gases with a molar ratio H2:CO ranging from 0.1 to 20, and at a temperature from 300°C to 500°C, characterized in that said mixtures are obtained under a pressure selected from 2,000 KPa and 16,000 KPa and with a catalyst based on chromium, zinc and at least one alkali metal.
2. A process as claimed in claim 1, wherein the molar ratio of H2:CO is in the range of from 0.1 to 20.
3. A process as claimed in claim 1, wherein the reaction temperature is carried out at from 350°C to 450°C.
4. A process as claimed in claim 1, wherein said mixtures are obtained under a pressure selected from 5,000 KPa and 13,000 KPa.
5. Process according to claim 1, wherein the mixtures have a methanol content comprised between 35% and 75% by weight on an anhydrous basis.
6. Process according to claim 1 or 5, wherein the ratio by weight of zinc to chromium, considered as their oxides, is comprised between 5/1 and 1/1.
7. Process according to claim 1 or 5, wherein the alkali metals considered as oxides are in an amount equal to 0.5%-5% by weight relative to the total of the elements taken as oxides.
8. Process according to claim 1, wherein the alkali metal is potassium.
9. Mixtures of methanol and higher alcohols prepared according to claim 1 or 5, corresponding to the following compositions on an anhydrous basis:
Methanol from 35% to 75% by weight Ethanol from 2% to 5% by weight Nor.propanol from 3% to 12% by weight Isobutanol from 10% to 30% by weight, and Higher alcohols with 5 or more C-atoms from 5% to 25% by weight.
Methanol from 35% to 75% by weight Ethanol from 2% to 5% by weight Nor.propanol from 3% to 12% by weight Isobutanol from 10% to 30% by weight, and Higher alcohols with 5 or more C-atoms from 5% to 25% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| IT24659A/80 | 1980-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1187109A true CA1187109A (en) | 1985-05-14 |
Family
ID=11214288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000385829A Expired CA1187109A (en) | 1980-09-15 | 1981-09-14 | Process for producing mixtures of methanol and higher alcohols and mixtures obtained thereby |
Country Status (32)
| Country | Link |
|---|---|
| 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 |
| WO2009088861A1 (en) * | 2008-01-04 | 2009-07-16 | University Of Southern California | 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 |
-
1980
- 1980-09-15 IT IT24659/80A patent/IT1193555B/en active
-
1981
- 1981-08-18 NZ NZ198082A patent/NZ198082A/en unknown
- 1981-08-19 GR GR65823A patent/GR74675B/el unknown
- 1981-08-20 AU AU74391/81A patent/AU546859B2/en not_active Ceased
- 1981-08-21 YU YU02024/81A patent/YU202481A/en unknown
- 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 RO RO105256A patent/RO83096B/en unknown
- 1981-09-08 DK DK396981A patent/DK396981A/en not_active Application Discontinuation
- 1981-09-08 PH PH26165A patent/PH17030A/en unknown
- 1981-09-08 BR BR8105777A patent/BR8105777A/en unknown
- 1981-09-08 KR KR1019810003346A patent/KR860000422B1/en active
- 1981-09-08 TR TR22083A patent/TR22083A/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 NO NO813093A patent/NO156007C/en unknown
- 1981-09-11 DE DE3136088A patent/DE3136088C2/en not_active Expired
- 1981-09-14 CA CA000385829A patent/CA1187109A/en not_active Expired
- 1981-09-14 BE BE0/205955A patent/BE890341A/en not_active IP Right Cessation
- 1981-09-14 CU CU8135516A patent/CU35516A/en unknown
- 1981-09-14 FR FR8117329A patent/FR2490215B1/en not_active Expired
- 1981-09-14 IE IE2127/81A patent/IE51556B1/en unknown
- 1981-09-14 AT AT0396981A patent/AT375062B/en not_active IP Right Cessation
- 1981-09-15 DD DD81233313A patent/DD201671A5/en unknown
- 1981-09-15 NL NL8104257A patent/NL8104257A/en not_active Application Discontinuation
- 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 CH CH5959/81A patent/CH651852A5/en not_active IP Right Cessation
- 1981-09-15 SE SE8105470A patent/SE8105470L/en unknown
- 1981-09-15 PL PL1981233029A patent/PL136284B1/en unknown
- 1981-09-15 CS CS816795A patent/CS221987B2/en unknown
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