CA1127188A - Process for the preparation of a hydrocarbon mixture, and hydrocarbon mixtures so prepared - Google Patents
Process for the preparation of a hydrocarbon mixture, and hydrocarbon mixtures so preparedInfo
- Publication number
- CA1127188A CA1127188A CA346,289A CA346289A CA1127188A CA 1127188 A CA1127188 A CA 1127188A CA 346289 A CA346289 A CA 346289A CA 1127188 A CA1127188 A CA 1127188A
- Authority
- CA
- Canada
- Prior art keywords
- oxygen
- compound
- boiling
- zinc
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
ABSTRACT
Hydrocarbons are prepared by contacting one or more oxygen-containing organic compounds with one or more zinc halides at elevated temperature in the presence of a high-boiling compound which has a melting point lower than the process temperature, and a vapour pressure at that temperature which is at the utmost 0.05 of the pressure of the oxygen-containing organic compound(s) and in which the oxygen-containing organic compound(s) and zinc halide are soluble.
Hydrocarbons are prepared by contacting one or more oxygen-containing organic compounds with one or more zinc halides at elevated temperature in the presence of a high-boiling compound which has a melting point lower than the process temperature, and a vapour pressure at that temperature which is at the utmost 0.05 of the pressure of the oxygen-containing organic compound(s) and in which the oxygen-containing organic compound(s) and zinc halide are soluble.
Description
~2~
A PROCESS FOR THE PREPARATION OF A HYDROCARHON
MIXTU~E, AND HYDROCARBON MIXTURES SO PREPARED
The invention relates to a process for the prepa-ration of a hydrocarbon ~ixturel in which one or more oxygen-containing organic compounds are cos~tacted with one or more zinc halides at elevated temperature.
Oxygen~containing compounds ~hich can be used in the process accordin~ to the invention are aliphatio alco-hols (in particular methanol), ethers (in particular dimethyl ether), ketones (in particular acetone), carbox~lic esters andJor aldehydes, for example aceta7-dehyde, carboxylic acids, for example acetic acid, poly-hydric alcohols and carboxylic anhydrides.
The starting materials containing the above-mentio-ned oxygen-oontaining co~pounds may Or course be obtai-ned from any usual source. Methanol derived from synthe-sis ga~ obtained from coal and ~ethanol prepared from natural ga~ for example, are extrsmely suitable.
A similar process to that ao¢ording to the present invention i9 known from U.S. patent specifi¢ations ~,059,646 and 4,059,647. Both patent specification~ des-cribe a proces~ for the preparation o~ triptane, in which ~ethanol, di~ethyl ether or mixtures thereof are contacted with zlnc bromide and zinc iodide, respecti-vely, at a temperature of 210-245C and 180-240 C, respectively.
According to the examples in said patent ~pecifi-oations, u~e i~ made of relatively lar~e quantities of zinc halide in relation to the quantlty of methanol to be converted.
It has now been ~ound that the quantity of zinc nalide required for the process can be drastically reduced, while the reaction ti~e i9 found to be short and a valuable hydrocarbon mixture is obtained, if the proce~s i3 carried out in the presence of a high-., :
. , .
l~Z71~
boiling compound which has a melting point which is lower than the temperature at which the process is carried out and a vapour pressure at said temperature which is at most 0.05 of the pressure of the oxygen-containing organic compound(s), and in which the oxygen-containing organic compoundts) and zinc halide are soluble.
The invention therefore relates to a process for the preparation of a hydrocarbon mixture, in which one or more oxygen-containing organio compounds are contacted with one or more zinc halides at elevated temperature, oharacterized in that the process is oarried out in the presence of a high-boiling oompound which has a melting point which is lower than the temperature at which the process is carried out and a vapour pressure at said temperature which is at most 0.05 of the pressure of the oxygen-containing organic compound(s), and in which the oxygen-containing organic compound(s) and zinc halide are soluble.
At the temperature at which the process is carried out the high-boiling compound preferably has a vapour pressure in the range from 10 3- 0.5 bar. In the case of a vapour pressure below 10 3 bar there is a great ohance that the compound is in the solid phase under the reaotion conditions. A vapour pressure in excess of 0.5 bar implies that the compound evaporates excessively under the reaction conditions. The high-boiling compounds whlch are suitable include the alco-hols having 10-23 C-atoms, such as dodeoanol, heptade-canol, nonadecanol and pentadecanol, further the ethers having 14-24 C-atoms, such as didodecyl ether, tetra-decyl tetracosanyl ether, dinonyl ether and dipentadecyl - ether and other high-boiling solvents having a boiling point above 210 C, which are liquid under the reaction - ' ~
~Z71138 conditions of the process according to the lnvention.
Of the alcohols heptadecanol is mo~t preferred.
Of the ethers most preference i9 given to didodecyl ether. The conversion of oxygen-containing organic compound(s) into hydrocarbons is found to be highest in the use of heptadecanol or didodecyl ether.
Good results are obtained if the quantity of high-boiling compound in relation to the quantity of zinc halide is 5-25% by weight.
Zinc iodide is preferably used on account of its great aotivity as zino halide. It has been established experimentally that a. a high-boiling oompound must be used to whioh applies that the solubility therein of zino halide at 100 C
is preferably at least 1 moltlitre. The process will prove to be economically unattractive if the solubi-lity is less than 1 mol/l.
b. The pres3ure at which the process is carried out is preferably in the range from 1 to 80 bar, at which pressure the organic oxygen compound to be converted must be present in the vapour phase. Operation of the process at pressures higher than 80 bar and below 1 bar is economically disadvantageous.
c. The temperature at which the process is carried out is preferably in the range from 170 to 250C. At temperatures below 170 C the conver~ion reaction proceeds too slowly.
Temperatures above 250C may adversely affect the oon-version prooe9s beoau9e undesired side-reaotions suoh as oraoking and oarbonization reaotions may take place, with the result that the yield of the desired hydrocar-bon mixture is affected unfavourably.
The proces~ acoording to the invention can also advantageously be carried out with zinc halide on a :
., - ~ . ..
llZ718B
carried, Por example silioa or alumina or compositions thereof. The process according to the invention can be carried out both batchwise and continuously.
Irrespective of the chosen process, a good degree of mixing or contact between the zinc halide and the org~nic oxygen compound(s) is important to obtain good results. It i9 possible to use any reaction system in which a high degree of mixing or contact between said compound(s) and zinc halide is obtained. Use can be made, for example, of systems having fixed beds or slurry reactors. The contact times are not of special importance and experts may vary these times to obtain optimum results which are also dependent on, for example, the volumes of the reactants, reactor type, temperature, etc. When use is made, for example, of a reactor with fixed bed and continuous flow of the reactants, contact times of about 0.5 to 100 minutes and even longer periods can be used. In batchwise operation the contact times may be considerably longer.
The invention will be further illustrated with reference to the following examples to which the invention is not limited, however.
EXAMPLE I
Quantities of 10.4 g of zinc iodide, 2.1 g (2.6 ml) f methanol and 0.2 g (0.25 ml) of heptadecanol were charged to a 200-ml autoclave, whereupon the autoclave was sealed airtight. The mixture was stirred and heated at 205C for 1 hour. The pressure rose to 13 bar. The reaotor was subsequently cooled to room temperature.
Gaseous product was disoharged lnto a gasometer. Liguid produat was distilled over at 160C from the reaotor to a cooled collecting vessel, initially at atmospheric pressure, while nitrogen wa~ blown through in order to promote the distillation (30 minutes), subsequently , ~127188 at reduced pressure (30 minuteq at 20 mm Hg, then 15 minutes at 2 mm Hg). The heptadecanol remained behind on the zinc iodide.
The liquid product in the cooled collecting vessel consisted of two layers, an aqueous layer and a layer of hydrocarbon oil. The bottom layer consisted mainly of water and less than O.ô8 ~ of methanol was present.
The layer of hydrocarbon oil, which had a weight of 0.53 g, had the following analysis:
~ by weight
A PROCESS FOR THE PREPARATION OF A HYDROCARHON
MIXTU~E, AND HYDROCARBON MIXTURES SO PREPARED
The invention relates to a process for the prepa-ration of a hydrocarbon ~ixturel in which one or more oxygen-containing organic compounds are cos~tacted with one or more zinc halides at elevated temperature.
Oxygen~containing compounds ~hich can be used in the process accordin~ to the invention are aliphatio alco-hols (in particular methanol), ethers (in particular dimethyl ether), ketones (in particular acetone), carbox~lic esters andJor aldehydes, for example aceta7-dehyde, carboxylic acids, for example acetic acid, poly-hydric alcohols and carboxylic anhydrides.
The starting materials containing the above-mentio-ned oxygen-oontaining co~pounds may Or course be obtai-ned from any usual source. Methanol derived from synthe-sis ga~ obtained from coal and ~ethanol prepared from natural ga~ for example, are extrsmely suitable.
A similar process to that ao¢ording to the present invention i9 known from U.S. patent specifi¢ations ~,059,646 and 4,059,647. Both patent specification~ des-cribe a proces~ for the preparation o~ triptane, in which ~ethanol, di~ethyl ether or mixtures thereof are contacted with zlnc bromide and zinc iodide, respecti-vely, at a temperature of 210-245C and 180-240 C, respectively.
According to the examples in said patent ~pecifi-oations, u~e i~ made of relatively lar~e quantities of zinc halide in relation to the quantlty of methanol to be converted.
It has now been ~ound that the quantity of zinc nalide required for the process can be drastically reduced, while the reaction ti~e i9 found to be short and a valuable hydrocarbon mixture is obtained, if the proce~s i3 carried out in the presence of a high-., :
. , .
l~Z71~
boiling compound which has a melting point which is lower than the temperature at which the process is carried out and a vapour pressure at said temperature which is at most 0.05 of the pressure of the oxygen-containing organic compound(s), and in which the oxygen-containing organic compoundts) and zinc halide are soluble.
The invention therefore relates to a process for the preparation of a hydrocarbon mixture, in which one or more oxygen-containing organio compounds are contacted with one or more zinc halides at elevated temperature, oharacterized in that the process is oarried out in the presence of a high-boiling oompound which has a melting point which is lower than the temperature at which the process is carried out and a vapour pressure at said temperature which is at most 0.05 of the pressure of the oxygen-containing organic compound(s), and in which the oxygen-containing organic compound(s) and zinc halide are soluble.
At the temperature at which the process is carried out the high-boiling compound preferably has a vapour pressure in the range from 10 3- 0.5 bar. In the case of a vapour pressure below 10 3 bar there is a great ohance that the compound is in the solid phase under the reaotion conditions. A vapour pressure in excess of 0.5 bar implies that the compound evaporates excessively under the reaction conditions. The high-boiling compounds whlch are suitable include the alco-hols having 10-23 C-atoms, such as dodeoanol, heptade-canol, nonadecanol and pentadecanol, further the ethers having 14-24 C-atoms, such as didodecyl ether, tetra-decyl tetracosanyl ether, dinonyl ether and dipentadecyl - ether and other high-boiling solvents having a boiling point above 210 C, which are liquid under the reaction - ' ~
~Z71138 conditions of the process according to the lnvention.
Of the alcohols heptadecanol is mo~t preferred.
Of the ethers most preference i9 given to didodecyl ether. The conversion of oxygen-containing organic compound(s) into hydrocarbons is found to be highest in the use of heptadecanol or didodecyl ether.
Good results are obtained if the quantity of high-boiling compound in relation to the quantity of zinc halide is 5-25% by weight.
Zinc iodide is preferably used on account of its great aotivity as zino halide. It has been established experimentally that a. a high-boiling oompound must be used to whioh applies that the solubility therein of zino halide at 100 C
is preferably at least 1 moltlitre. The process will prove to be economically unattractive if the solubi-lity is less than 1 mol/l.
b. The pres3ure at which the process is carried out is preferably in the range from 1 to 80 bar, at which pressure the organic oxygen compound to be converted must be present in the vapour phase. Operation of the process at pressures higher than 80 bar and below 1 bar is economically disadvantageous.
c. The temperature at which the process is carried out is preferably in the range from 170 to 250C. At temperatures below 170 C the conver~ion reaction proceeds too slowly.
Temperatures above 250C may adversely affect the oon-version prooe9s beoau9e undesired side-reaotions suoh as oraoking and oarbonization reaotions may take place, with the result that the yield of the desired hydrocar-bon mixture is affected unfavourably.
The proces~ acoording to the invention can also advantageously be carried out with zinc halide on a :
., - ~ . ..
llZ718B
carried, Por example silioa or alumina or compositions thereof. The process according to the invention can be carried out both batchwise and continuously.
Irrespective of the chosen process, a good degree of mixing or contact between the zinc halide and the org~nic oxygen compound(s) is important to obtain good results. It i9 possible to use any reaction system in which a high degree of mixing or contact between said compound(s) and zinc halide is obtained. Use can be made, for example, of systems having fixed beds or slurry reactors. The contact times are not of special importance and experts may vary these times to obtain optimum results which are also dependent on, for example, the volumes of the reactants, reactor type, temperature, etc. When use is made, for example, of a reactor with fixed bed and continuous flow of the reactants, contact times of about 0.5 to 100 minutes and even longer periods can be used. In batchwise operation the contact times may be considerably longer.
The invention will be further illustrated with reference to the following examples to which the invention is not limited, however.
EXAMPLE I
Quantities of 10.4 g of zinc iodide, 2.1 g (2.6 ml) f methanol and 0.2 g (0.25 ml) of heptadecanol were charged to a 200-ml autoclave, whereupon the autoclave was sealed airtight. The mixture was stirred and heated at 205C for 1 hour. The pressure rose to 13 bar. The reaotor was subsequently cooled to room temperature.
Gaseous product was disoharged lnto a gasometer. Liguid produat was distilled over at 160C from the reaotor to a cooled collecting vessel, initially at atmospheric pressure, while nitrogen wa~ blown through in order to promote the distillation (30 minutes), subsequently , ~127188 at reduced pressure (30 minuteq at 20 mm Hg, then 15 minutes at 2 mm Hg). The heptadecanol remained behind on the zinc iodide.
The liquid product in the cooled collecting vessel consisted of two layers, an aqueous layer and a layer of hydrocarbon oil. The bottom layer consisted mainly of water and less than O.ô8 ~ of methanol was present.
The layer of hydrocarbon oil, which had a weight of 0.53 g, had the following analysis:
~ by weight
2-methyl propane 0.72 n-butane 1.23 2,2-dimethyl propane o.64 2-methyl butane 1.77 n-pentane 1.90 2,2-dimethyl butane 0.02 2,3-dimethyl butane 1.35 2-methyl pentane 0.36
3-methyl pentane 0.28 n-hexane 0.14 2,2,3-trimethyl butene-1 5.72 2,4-dimethyl pentane 0.37 2,2,3-trimethyl butane 17.8 2,3-dimethyl pentane 0.72 2-methyl hexane 0.18 3-methyl hexane 0.21 n-heptane 0.64 butenes 0.42 pentene~ 2.27 hexeneq 0.52 heptenes 1.12 octeneq 1.40 2,2,4-trimethyl pentane 0.31 2,2,3,3-tetramethyl butane 0.46 2,5-dimethyl hexane 0.31 llZ~
2,2-dimethyl hexane 0.33 2~2,3-trimethyl pentane 11.83 3,3-dimethyl hexane 0.81 2,3,4-trimethyl pentane 0.69 2,3,3-trimethyl pentane 1.41 3,4-dimethyl hexane 0.25 n-octane 43.81 Total 100 EXAMPLE II
In this experiment use was made of a catalyst consisting of ZnI2/heptadecanol on a carrier of silica spheres having an average diameter of 15 nm and pores with an average diameter of 2.5 nm- This catalyst was prepared as follows:
100 g of ZnI2 was dissolved in 60 ml of methanol, to which 5 g of heptadecanol was subsequently added. To this solution 100 g of siica in the above-mentioned form was added so that the silica was impregnated with the solution. The catalyst material was subsequently dried at 120C.
For the experiment 20.3 g of said catalyst and 2.1 g (2.6 ml) of methanol were charged to a 200-ml autoclave, where-upon the autoclave was sealed airtight. The mixture was stirred and heated at 205C for 1 hour. The pressure rose to 15 bar.
The reactor was subsequently cooled to room temperature.
Gaseous product was discharged into a gasometer.
Liquid product was distilled over at 160C from the reactor to a cooled collecting vessel, initially at atmospheric pressure, while nitrogen was blown through as in Lxample I ~30 minutes), subsequent-ly at reduced pressure (30 minutes at 20 mm Hg, subsequçntly 15 minutes at 2 mm Hg). The heptadecanol remained behind on the zinc .:
. : .
llZ7188 iodide.
The liquid product in the cooled collecting ~essel consisted of two layers, an aqueous layer and a layer of hydrocarbon oil. The bottom layer consisted mainly of water and les~ than 0.3 g of methanol was present. The layer of hydrocarbon oil, which had a weight of o.8 g, had the following analysi~:
S by weight 2-methyl propane 1.18 n-butane 0.87 2,2-dimethyl propane 0.82 2-methyl butane 1.06 n-pentane 2.16 2,2-dimethyl butane 0.03 2,3-dimethyl butane 0.64 2-methyl pentane 0.21 3-methyl pentane 0.16 n-hexane 0.16 2,2,3-trimethyl butene-1 4.56 2,4-dimethyl pentane 2,2,3-trimethyl butane 8.07 2,3-dimethyl pentane 0.32 2-methyl hexane 0.20 3-methyl hexane 0.15 n-heptane 0.52 butenes 0.52 pentenes 2.16 hexenes 0.41 heptenes 1.03 ootenes 0 95 2,2,4-trimethyl pentane 0.14 2,2,3,3-tetramethyl butane 0.38 2,5-dimethyl hexane 0.13 2,2-dimethyl hexane 0.26 2,2,3-trimethyl pentane 23.1 :
;
.
11271~8 3,3-dimethyl hexane 0.37 2,3,4-trimethyl pentane 0~34 2,3,3-trimethyl pentane 0.99 3,4-dimethyl hexane 0.11 n-octane 48.1 Total 100 EXAMPLE III
Quantities of 10.4 g of zinc iodide and 0.2 g (0.25 ml) of heptadecanol were charged to a 200-ml autoclave and subsequent-ly 1.51 g of dimethyl ether was supplied to the autoclave at apressure of 5 bar at room temperature.
The mixture was stirred and heated at 205C for 1.5 hours. The pressure rose to 12 bar. The reaction product was worked up in the same manner as in Example I.
A layer of hydrocarbon oil having a weight of 0.92 g was formed, which layer was not analysed further.
EXAMPLE IV
Quantities of 10.4 g of zinc iodide, 2.1 g ~2.6 ml) of acetone and 0.2 g ~ 0.25 ml) of heptadecanol were charged to an autoclave under nitrogen, whereupon the autoclave was sealed air tight.
The pressure rose to 9 bar and the mixture was stirred and heated at about 180C for 1 hour. The reactor was subsequent-ly cooled to room temperature. Gaseous product was discharged into a gasometer. Liquid product was distilled over at 160C from the reactor to a cooled collecting vessel, initially at atmospheric pressure, while nitrogen was blown through as in Example I (30 ; minutes), and subsequently at reduced pressure ~30 minutes at 20 mm Hg and subsequently 15 minutes at 2 mm Hg). The material B~ 8 remaining in the autoclave was removed by washing with water.
The quantity of gaseous product was small and consisted mainly of isoparaffins. The liquid product present - 8a -B
.
. . . . . . . ... . .
,. , . . . . .. . ~.
....
i.
. ~ .; .
: . `
112''~188 g in the cooled collecting vessel consisted of two layers, an aqueous layer and a layer of hydrocarbon oil. The layer of hydrocarbon oil, wh~ch was not analysed, had a weight of o.8 g.
COMPARATIVE EXPERIMENT
In order to demonstrate the effect of the high-boiling compound on the degree of conver~ion of the oxygen-contai-ning compound(s) a co~parative experiment was carried out which differs from the experiment of Example I only in the fact that no high-boiling compound wa~ used.
After the produot had been processed, it was found that no detectable quantity of hydrocarbon oil had formed.
: - :. . ' :' ;' ~ ` :' . ~: , .
2,2-dimethyl hexane 0.33 2~2,3-trimethyl pentane 11.83 3,3-dimethyl hexane 0.81 2,3,4-trimethyl pentane 0.69 2,3,3-trimethyl pentane 1.41 3,4-dimethyl hexane 0.25 n-octane 43.81 Total 100 EXAMPLE II
In this experiment use was made of a catalyst consisting of ZnI2/heptadecanol on a carrier of silica spheres having an average diameter of 15 nm and pores with an average diameter of 2.5 nm- This catalyst was prepared as follows:
100 g of ZnI2 was dissolved in 60 ml of methanol, to which 5 g of heptadecanol was subsequently added. To this solution 100 g of siica in the above-mentioned form was added so that the silica was impregnated with the solution. The catalyst material was subsequently dried at 120C.
For the experiment 20.3 g of said catalyst and 2.1 g (2.6 ml) of methanol were charged to a 200-ml autoclave, where-upon the autoclave was sealed airtight. The mixture was stirred and heated at 205C for 1 hour. The pressure rose to 15 bar.
The reactor was subsequently cooled to room temperature.
Gaseous product was discharged into a gasometer.
Liquid product was distilled over at 160C from the reactor to a cooled collecting vessel, initially at atmospheric pressure, while nitrogen was blown through as in Lxample I ~30 minutes), subsequent-ly at reduced pressure (30 minutes at 20 mm Hg, subsequçntly 15 minutes at 2 mm Hg). The heptadecanol remained behind on the zinc .:
. : .
llZ7188 iodide.
The liquid product in the cooled collecting ~essel consisted of two layers, an aqueous layer and a layer of hydrocarbon oil. The bottom layer consisted mainly of water and les~ than 0.3 g of methanol was present. The layer of hydrocarbon oil, which had a weight of o.8 g, had the following analysi~:
S by weight 2-methyl propane 1.18 n-butane 0.87 2,2-dimethyl propane 0.82 2-methyl butane 1.06 n-pentane 2.16 2,2-dimethyl butane 0.03 2,3-dimethyl butane 0.64 2-methyl pentane 0.21 3-methyl pentane 0.16 n-hexane 0.16 2,2,3-trimethyl butene-1 4.56 2,4-dimethyl pentane 2,2,3-trimethyl butane 8.07 2,3-dimethyl pentane 0.32 2-methyl hexane 0.20 3-methyl hexane 0.15 n-heptane 0.52 butenes 0.52 pentenes 2.16 hexenes 0.41 heptenes 1.03 ootenes 0 95 2,2,4-trimethyl pentane 0.14 2,2,3,3-tetramethyl butane 0.38 2,5-dimethyl hexane 0.13 2,2-dimethyl hexane 0.26 2,2,3-trimethyl pentane 23.1 :
;
.
11271~8 3,3-dimethyl hexane 0.37 2,3,4-trimethyl pentane 0~34 2,3,3-trimethyl pentane 0.99 3,4-dimethyl hexane 0.11 n-octane 48.1 Total 100 EXAMPLE III
Quantities of 10.4 g of zinc iodide and 0.2 g (0.25 ml) of heptadecanol were charged to a 200-ml autoclave and subsequent-ly 1.51 g of dimethyl ether was supplied to the autoclave at apressure of 5 bar at room temperature.
The mixture was stirred and heated at 205C for 1.5 hours. The pressure rose to 12 bar. The reaction product was worked up in the same manner as in Example I.
A layer of hydrocarbon oil having a weight of 0.92 g was formed, which layer was not analysed further.
EXAMPLE IV
Quantities of 10.4 g of zinc iodide, 2.1 g ~2.6 ml) of acetone and 0.2 g ~ 0.25 ml) of heptadecanol were charged to an autoclave under nitrogen, whereupon the autoclave was sealed air tight.
The pressure rose to 9 bar and the mixture was stirred and heated at about 180C for 1 hour. The reactor was subsequent-ly cooled to room temperature. Gaseous product was discharged into a gasometer. Liquid product was distilled over at 160C from the reactor to a cooled collecting vessel, initially at atmospheric pressure, while nitrogen was blown through as in Example I (30 ; minutes), and subsequently at reduced pressure ~30 minutes at 20 mm Hg and subsequently 15 minutes at 2 mm Hg). The material B~ 8 remaining in the autoclave was removed by washing with water.
The quantity of gaseous product was small and consisted mainly of isoparaffins. The liquid product present - 8a -B
.
. . . . . . . ... . .
,. , . . . . .. . ~.
....
i.
. ~ .; .
: . `
112''~188 g in the cooled collecting vessel consisted of two layers, an aqueous layer and a layer of hydrocarbon oil. The layer of hydrocarbon oil, wh~ch was not analysed, had a weight of o.8 g.
COMPARATIVE EXPERIMENT
In order to demonstrate the effect of the high-boiling compound on the degree of conver~ion of the oxygen-contai-ning compound(s) a co~parative experiment was carried out which differs from the experiment of Example I only in the fact that no high-boiling compound wa~ used.
After the produot had been processed, it was found that no detectable quantity of hydrocarbon oil had formed.
: - :. . ' :' ;' ~ ` :' . ~: , .
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a hydrocarbon mixture, in which one or more oxygen-containing organic compounds in the vapour phase are contacted with one or more zinc halides at elevated temperature in the presence of a high-boiling compound which has a melting point which is lower than the temperature at which the process is carried out, and a vapour pressure at said temperature which is at most 0.05 of the pressure of the oxygen-containing organic compound(s), and in which the oxygen-containing organic compound(s) and zinc halide are soluble.
2. A process as claimed in claim 1, characterized in that the high-boiling compound has a vapour pressure in the range from 10-3-0.5 bar at a temperature at which the process is carried out.
3. A process as claimed in claim 1 or 2, characterized in that a high-boiling compound is used to which applies that the solubility therein of zinc halide at 100°C is at least 1 mol/l.
4. A process as claimed in claim 1, characterized in that the high-boiling compound belongs to the group consisting of alcohols having 10-23 C-atoms, ethers having 14-24 C-atoms, and other high-boiling solvents having a boiling point above 210 C.
5. A process as claimed in claim 4, characterized in that heptadecanol is used.
6. A process as claimed in claim 4, characterized in that didodecyl ether is used.
7. A process as claimed in claim 1 or 4,characterized in that the quantity of high-boiling compound is 5-25% by weight in relation to the quantity of zinc halide.
8. A process as claimed in claim 1, characterized in that the zinc halide used is zinc iodide.
9. A process as claimed in claim 1 or 8, characterized in that the zinc halide is deposited on a carrier containing silica and/or alumina.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7902886 | 1979-04-12 | ||
| NL7902886A NL7902886A (en) | 1979-04-12 | 1979-04-12 | METHOD FOR PREPARING A HYDROCARBON MIXTURE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127188A true CA1127188A (en) | 1982-07-06 |
Family
ID=19832974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA346,289A Expired CA1127188A (en) | 1979-04-12 | 1980-02-22 | Process for the preparation of a hydrocarbon mixture, and hydrocarbon mixtures so prepared |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4249031A (en) |
| EP (1) | EP0018032B1 (en) |
| JP (1) | JPS56890A (en) |
| CA (1) | CA1127188A (en) |
| DE (1) | DE3062254D1 (en) |
| NL (1) | NL7902886A (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4593147A (en) * | 1984-11-01 | 1986-06-03 | Air Products And Chemicals, Inc. | Synthesis of neoalkanes |
| JPS61196809A (en) * | 1985-02-26 | 1986-09-01 | Honda Motor Co Ltd | Suspension of vehicles for driving across uneven ground |
| DK1363866T3 (en) * | 2001-03-02 | 2008-08-11 | Bp Oil Int | Process and apparatus for producing triptan and / or tripten |
| US7838708B2 (en) * | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| US20050038310A1 (en) * | 2003-07-15 | 2005-02-17 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| US20050171393A1 (en) * | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| US7674941B2 (en) * | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US20080275284A1 (en) * | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US7883568B2 (en) * | 2006-02-03 | 2011-02-08 | Grt, Inc. | Separation of light gases from halogens |
| KR101368416B1 (en) | 2006-02-03 | 2014-03-05 | 리액션 35, 엘엘씨 | Continuous process for converting natural gas to liquid hydrocarbons |
| JP2010501679A (en) * | 2006-08-24 | 2010-01-21 | カリフォルニア インスティテュート オブ テクノロジー | Process for producing hydrocarbons |
| US8921625B2 (en) * | 2007-02-05 | 2014-12-30 | Reaction35, LLC | Continuous process for converting natural gas to liquid hydrocarbons |
| WO2008143940A2 (en) * | 2007-05-14 | 2008-11-27 | Grt, Inc. | Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen |
| CN101765574A (en) * | 2007-05-24 | 2010-06-30 | Grt公司 | Zone reactor incorporating reversible hydrogen halide capture and release |
| EP2060550A1 (en) | 2007-11-16 | 2009-05-20 | BP p.l.c. | Process for producing triptane |
| EP2060551A1 (en) | 2007-11-16 | 2009-05-20 | BP p.l.c. | Process for producing triptane |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| WO2010124041A1 (en) * | 2009-04-22 | 2010-10-28 | Grt, Inc. | Process for converting hydrocarbon feedstocks with electrolytic and photoelectrocatalytic recovery of halogens |
| US8198495B2 (en) * | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2492984A (en) * | 1946-05-31 | 1950-01-03 | Houdry Process Corp | Organic reactions |
| US3969427A (en) * | 1974-11-19 | 1976-07-13 | Mobil Oil Corporation | Conversion of alcohols and/or ethers to hydrocarbons |
| US4059646A (en) * | 1975-10-02 | 1977-11-22 | Shell Oil Company | Process for producing triptane by contacting methanol or dimethyl ether with zinc bromide |
| US4059647A (en) * | 1975-10-02 | 1977-11-22 | Shell Oil Company | Process for producing triptane by contacting methanol or dimethyl ether with zinc chloride |
| GB1547955A (en) * | 1977-11-04 | 1979-07-04 | Shell Int Research | Process for the production of a hydrocarbon mixture containing 2,3,3-trimenthyl butyne |
| DE2750609A1 (en) * | 1977-11-11 | 1979-05-17 | Shell Int Research | Hydrocarbon mixtures contg. tri:methyl-butane - prepared by contacting methanol and-or di:methyl ether with zinc iodide or bromide at elevated temp. |
| US4126642A (en) * | 1977-11-14 | 1978-11-21 | Shell Oil Company | Conversion of butadiene (1,3) and methanol |
| FR2409249A1 (en) * | 1977-11-21 | 1979-06-15 | Shell Int Research | Hydrocarbon mixtures contg. tri:methyl-butane - prepared by contacting methanol and-or di:methyl ether with zinc iodide or bromide at elevated temp. |
| US4166189A (en) * | 1978-04-24 | 1979-08-28 | Shell Oil Company | Production of methyl esters by contacting methanol or dimethyl ether with carbon monoxide and zinc iodide |
-
1979
- 1979-04-12 NL NL7902886A patent/NL7902886A/en not_active Application Discontinuation
-
1980
- 1980-02-22 CA CA346,289A patent/CA1127188A/en not_active Expired
- 1980-03-25 US US06/133,704 patent/US4249031A/en not_active Expired - Lifetime
- 1980-04-01 DE DE8080200303T patent/DE3062254D1/en not_active Expired
- 1980-04-01 EP EP80200303A patent/EP0018032B1/en not_active Expired
- 1980-04-09 JP JP4577580A patent/JPS56890A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0018032B1 (en) | 1983-03-09 |
| EP0018032A1 (en) | 1980-10-29 |
| DE3062254D1 (en) | 1983-04-14 |
| US4249031A (en) | 1981-02-03 |
| JPS56890A (en) | 1981-01-07 |
| NL7902886A (en) | 1980-10-14 |
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