US3022359A - Selective hydrogenation of cyclododecatriene to cyclododecene - Google Patents
Selective hydrogenation of cyclododecatriene to cyclododecene Download PDFInfo
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- US3022359A US3022359A US804606A US80460659A US3022359A US 3022359 A US3022359 A US 3022359A US 804606 A US804606 A US 804606A US 80460659 A US80460659 A US 80460659A US 3022359 A US3022359 A US 3022359A
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- cyclododecatriene
- cyclododecene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Definitions
- the present invention relates to an improved process for the selective hydrogenation of a polyolefin or an acetylene to an olefinic material more highly saturated than the starting material. More particularly, the present invention relates to hydrogenating this more highly unsaturated than a monoolefin material with a high surface area catalyst in the presence of a displacement solvent to obtain a selective hydrogenation to the desired materials.
- this displacement solvent is strongly adsorbed on the high surface area catalyst thus obtaining a selective displacement from the catalyst surface of the less strongly adsorbed monoolefins preferentially to the more strongly adsorbed more highly unsaturated feed material.
- the hydrogen may be supplied as gaseous hydrogen, as a hydrogen transfer agent, or as gaseous hydrogen plus a hydrogen transfer agent.
- the present invention relates to selectively hydrogenating cyclododecatriene to cyclododecene utilizing only a secondary alcohol both to supply the hydrogen and to produce the displacement solvent in situ.
- the alcohol acts both as a hydrogen transfer agent and additionally is converted to a ketone said ketone then acting as the displacement solvent.
- the 1,5,9-cyclododecatriene preferred material to be selectively hydrogenated according to this invention is known in the art, being prepared by trimerizing butadiene with alkyl metal type catalysts. Its preparation and description is described for example in Angewandte Chemie, V. 69, No. 112397 (June 7, 1957). Although four stereo isomers of 1,5,9-cyclododecatriene are theoretically possible only two have thus far been isolated. These are the "ice cis, trans, trans (cis., tr., tr.) and the trans, trans, trans (tr., tr., tr.) as shown by the formulas below.
- materials more unsaturated than olefins such as triolefins, conjugated and unconjugated diolefins, cyclic diolefins, aromatics and acetylenes can be selectively hydrogenated to more saturated compounds of a particular unsaturation type such as monoolefins, diolefins, etc.
- diolefins and acetylenes may be converted to olefins and triolefins can be converted to diolefins or to monoolefins whichever product is desired. This is possible merely by selecting the proper displacing agent and stoichiometric amounts of hydrogen.
- the present invention process will be useful also in selectively hydrogenating mixtures of unsaturated and saturated materials, such as, for example, in gasolines of undesirable acetylenes and diolefins to olefins, thus increasing the stability of the gasoline without decreasing the octane number thereof. In prior art hydrogenations this couldonly be done at the expense of converting considerable amounts of high octane olefins to low octane parafiins.
- the feed stocks which may be utilized in the present invention will preferably be C to C unsaturates.
- the high surface area catalysts used may be nickel such as Raney nickel or nickel deposited on kieselguhr, alumina or silica. Other materials such as iron, cobalt, copper,
- ketones or aldehydes (2) amine type compounds such as pyridine, piperidine, mono and dimethyl aniline, (3) phenol type compounds such as phenol, hydroquinone, naphthol and cresol and (4) ether type compounds such as dialkyl ethers, dioxane, tetrahydrofuran, and (5) nitriles.
- these materials should be lower molecuar weight materials in the range of C -C Most preferably, it is preferred to utilize acetone or methyl ethyl ketone.
- the amount of displacement solvent utilized should be at least sutficient to saturate the catalyst in the absence of other materials.
- amounts of the displacement solvent should be in the range of less than 1 to greater than 100% based upon the olefinic material to be hydrogenated. It should be noted that although a large number of different feed stocks may be hydrogenated according to this invention that the displacement solvent need only be selected to displace the mono or diolefins from the catalyst and therefore generally the same solvents can be utilized regardless of the feed stock being treated. Reaction temperatures will range from 20-400 C., preferably 120-250 C. and pressures may be from 1-100 atmospheres. In most cases it will be preferred to utilize enough pressure to obtain a liquid phase reaction of the reactants.
- gaseous hydrogen as the source of hydrogen it is preferred to employ temperatures in the range of 20- 250 C. preferably 100 to 200 C. and pressures of from 1 to 100 atmospheres. Any of the displacing solvents mentioned above can be employed. In the case of acetone or methylethyl ketone a mixture of the alcohol and corresponding ketone can also be employed. A ratio of ketone to alcohol must be selected such that the rate of hydrogen transfer is negligible compared to the rate of hydrogenation; that is the rate of addition of gaseous hydrogen to the double bond. This is more clearly demonstrated by a few rate data at 170 C. using Raney' nickel as catalyst, isopropyl alcohol as hydrogen donor and cyclododecatriene as the unsaturated compound. The rates of hydrogen transfer as a function of the amount of isopropanol converted to acetone are as follows.
- the preferred hydrogen donors utilized are alcohols (primary or preferably secondary alcohols), tetralin or other partially or completely hydrogenated fused ring aromatic hydrocarbons or single ring partially or fully hydrogenated aromatics.
- the hydrogen donor will be cyclododecanol, cyclohexanol, secondary butanol or isopropanol or materials which produce a selective solvent in situ.
- pressurization is preferred to maintain these materials in their liquid state at reaction temperatures.
- R and R may be alkyl or aryl groups or may be joined to form a ring compound.
- secondary alcohol is convertedto a ketone.
- this ketone can be rehydrogenated to the alcohol to obtain a continuous process, alternatively it may be preferred to utilize the ketone as such in other processes or for sale as a final product.
- a particular advantage of the use of hydrogen donors to supply hydrogen to the process is that this provides an efficient economical control of the amount of hydrogen added so as to obtain the selective hydrogenation desired. Thus, approximately stoichiometric amounts of the hydrogen transfer agent are used to obtain the saturation desired. Utilizing hydrogen donor reactants temperatures in the range of 100400 C. preferably l20-250 C. and pressures of from l20 atmospheres are preferred. It is also contemplated that mixtures of a hydrogen transfer agent and a separate displacing solvent may be used.
- temperatures will be in the range of 20400 C. and pressures will be in the range of l-lOO atmospheres.
- An advantage for the use of both hydrogen transfer agents and gaseous hydrogen is that in case one does not want to continuously remove acetone when using isopropanol and at the same time maintain a high rate of hydrogenation, gaseous hydrogen can be added as soon as the hydrogen transfer rate becomes too slow form an economic standpoint.
- Example 1 was flushed with nitrogen, pressured to 300500 p.s.i.g.
- the process for the selective hydrogenation of a C -C hydrocarbon more unsaturated than a monoolefin to an olefinic C -C hydrocarbon more saturated than the starting material which comprises reacting the more unsaturated hydrocarbon with at least the stoichiometric amount of a hydrogen source selected from the group consisting of C -C saturated aliphatic monohydric alcohols, C -C saturated cyclic monohydric alcohols, and mixtures of each of these materials with gaseous hydrogen to obtain hydrogenation to the desired olefinic material in the presence of a high surface area hydrogenation catalyst.
- a hydrogen source selected from the group consisting of C -C saturated aliphatic monohydric alcohols, C -C saturated cyclic monohydric alcohols, and mixtures of each of these materials with gaseous hydrogen to obtain hydrogenation to the desired olefinic material in the presence of a high surface area hydrogenation catalyst.
Description
ilnited States SELECTIVE HYDROGENATTQN F CYCLODG- DECATRHENE TO (lYKILGDUDECENE Herbert K. Wiese, Cranford, and fiamuel B. Lippincott,
Springfield, NJ, assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Apr. 7, 1959, Ser. No. 804,6ll6
18 Claims. ((311. 260-666) The present invention relates to an improved process for the selective hydrogenation of a polyolefin or an acetylene to an olefinic material more highly saturated than the starting material. More particularly, the present invention relates to hydrogenating this more highly unsaturated than a monoolefin material with a high surface area catalyst in the presence of a displacement solvent to obtain a selective hydrogenation to the desired materials. Although it is not intended to limit this'invention to any mechanism for its accomplishment, it is theorized that this displacement solvent is strongly adsorbed on the high surface area catalyst thus obtaining a selective displacement from the catalyst surface of the less strongly adsorbed monoolefins preferentially to the more strongly adsorbed more highly unsaturated feed material. This, of course, produces the desired selective hydrogenation to olefins rather than to paraflins. In separate preferred embodiments the hydrogen may be supplied as gaseous hydrogen, as a hydrogen transfer agent, or as gaseous hydrogen plus a hydrogen transfer agent. Most particularly, the present invention relates to selectively hydrogenating cyclododecatriene to cyclododecene utilizing only a secondary alcohol both to supply the hydrogen and to produce the displacement solvent in situ. Thus, the alcohol acts both as a hydrogen transfer agent and additionally is converted to a ketone said ketone then acting as the displacement solvent.
Prior to the present it has been known that all attempts to hydrogenate materials such as cyclic trienes, aromatics and diolefins with or without metallic catalysts invariably resulted in a comparatively non-selective hydrogenation to a mixture of saturated and unsaturated materials. Additionally, with respect to materials such as cyclododecatriene, which contains 1 cis double bond and 2 trans double bonds in its most commonly prepared form, it was found that the cis double bond hydrogenated faster than the trans double bonds. Thus, when it was attempted to obtain cyclododecene, cyclododecadiene preferentially to cyclododecene was obtained along with cyclododecane. Surprisingly, a method has now been developed Which can be used to obtain selective hydrogenation as, for example, of cyclododecatriene to cyclododecene in very high yields in the order of selectivities of at least 86% along with conversions of about 95%.
The 1,5,9-cyclododecatriene preferred material to be selectively hydrogenated according to this invention is known in the art, being prepared by trimerizing butadiene with alkyl metal type catalysts. Its preparation and description is described for example in Angewandte Chemie, V. 69, No. 112397 (June 7, 1957). Although four stereo isomers of 1,5,9-cyclododecatriene are theoretically possible only two have thus far been isolated. These are the "ice cis, trans, trans (cis., tr., tr.) and the trans, trans, trans (tr., tr., tr.) as shown by the formulas below.
Throughout this specification it will be assumed that either of the isomers above represented or of the other isomers may be utilized or mixtures thereof.
According to the present invention it is contemplated that materials more unsaturated than olefins such as triolefins, conjugated and unconjugated diolefins, cyclic diolefins, aromatics and acetylenes can be selectively hydrogenated to more saturated compounds of a particular unsaturation type such as monoolefins, diolefins, etc. Thus, diolefins and acetylenes may be converted to olefins and triolefins can be converted to diolefins or to monoolefins whichever product is desired. This is possible merely by selecting the proper displacing agent and stoichiometric amounts of hydrogen. Since monoolefins are less strongly adsorbed than diolefins and diolefins are less strongly adsorbed than triolefins it is necessary for example, if one wants to hydrogenate a triolefin to a diolefin, to select a displacing agent that selectively desorbs the diolefins as soon as they are formed from the triolefins. It should be noted that in each case selective hydrogenation to the desired compound is obtained rather than bydrogenation to obtain a mixture of saturated and unsaturated compounds. It is further contemplated that the present invention process will be useful also in selectively hydrogenating mixtures of unsaturated and saturated materials, such as, for example, in gasolines of undesirable acetylenes and diolefins to olefins, thus increasing the stability of the gasoline without decreasing the octane number thereof. In prior art hydrogenations this couldonly be done at the expense of converting considerable amounts of high octane olefins to low octane parafiins.
The feed stocks which may be utilized in the present invention will preferably be C to C unsaturates. The high surface area catalysts used may be nickel such as Raney nickel or nickel deposited on kieselguhr, alumina or silica. Other materials such as iron, cobalt, copper,
, palladium, platinum, molybdenum, tungsten and chromium as well as their oxides or sulfides may also be utilized alone or disposed on high surface area bases. These high surface area catalysts have surface areas in the range of 1-500, preferably 5-100 sq. meters per gram. The organic displacement solvents which are more strongly adsorbed on the catalyst than are the monoolefins which may be utilized in this invention are as follows (listed in the order in which they are preferred): (1)
ketones or aldehydes, (2) amine type compounds such as pyridine, piperidine, mono and dimethyl aniline, (3) phenol type compounds such as phenol, hydroquinone, naphthol and cresol and (4) ether type compounds such as dialkyl ethers, dioxane, tetrahydrofuran, and (5) nitriles. Preferably these materials should be lower molecuar weight materials in the range of C -C Most preferably, it is preferred to utilize acetone or methyl ethyl ketone. The amount of displacement solvent utilized should be at least sutficient to saturate the catalyst in the absence of other materials. Preferably amounts of the displacement solvent should be in the range of less than 1 to greater than 100% based upon the olefinic material to be hydrogenated. It should be noted that although a large number of different feed stocks may be hydrogenated according to this invention that the displacement solvent need only be selected to displace the mono or diolefins from the catalyst and therefore generally the same solvents can be utilized regardless of the feed stock being treated. Reaction temperatures will range from 20-400 C., preferably 120-250 C. and pressures may be from 1-100 atmospheres. In most cases it will be preferred to utilize enough pressure to obtain a liquid phase reaction of the reactants. It is preferred to utilize stoichiometric amounts of the hydrogen source supplied whether in the form of gaseous hydrogen or as a hydrogen transfer agent, to obtain the desired hydrogenation of one double bond or of two double bonds. Alternatively, of course, it is also contemplated that excess hydrogen as gaseous hydrogen or hydrogen donor material may be utilized with limitation of reaction times to obtain the desired amount of hydrogenation, i. e. hydrogenation of one double bond or of two double bonds only. For example, when using isopropanol as hydrogen donor the rate of hydrogen transfer slows down as the acetone builds up in the reaction mixture. Therefore, if no provision is made for continuously removing the acetone, for example by continuously distilling off the acetone, an excess of isopropanol over the stoichiometric amount is desirable from the standpoint of maintaining a high rate of hydrogen transfer.
Utilizing gaseous hydrogen as the source of hydrogen it is preferred to employ temperatures in the range of 20- 250 C. preferably 100 to 200 C. and pressures of from 1 to 100 atmospheres. Any of the displacing solvents mentioned above can be employed. In the case of acetone or methylethyl ketone a mixture of the alcohol and corresponding ketone can also be employed. A ratio of ketone to alcohol must be selected such that the rate of hydrogen transfer is negligible compared to the rate of hydrogenation; that is the rate of addition of gaseous hydrogen to the double bond. This is more clearly demonstrated by a few rate data at 170 C. using Raney' nickel as catalyst, isopropyl alcohol as hydrogen donor and cyclododecatriene as the unsaturated compound. The rates of hydrogen transfer as a function of the amount of isopropanol converted to acetone are as follows.
\ Rate of gaseous hydrogen addition to cyclododecatriene. 7
Although the absolute rates vary with each batch of nickel the relative rates remain about the same. .It is evident from these data that a :50 or greater mixture of acetone: isopropanol can be used as displacing solvent when using gaseous hydrogen as the source of hydrogen.
The preferred hydrogen donors utilized are alcohols (primary or preferably secondary alcohols), tetralin or other partially or completely hydrogenated fused ring aromatic hydrocarbons or single ring partially or fully hydrogenated aromatics. Most preferably the hydrogen donor will be cyclododecanol, cyclohexanol, secondary butanol or isopropanol or materials which produce a selective solvent in situ. With isopropyl and with secondary butyl alcohol hydrogen donors, pressurization is preferred to maintain these materials in their liquid state at reaction temperatures.
The reaction when using a secondary alcohol as hydrogen donor may be illustrated by the following equation.
Q 2RCHOHR') Q In the above equation R and R may be alkyl or aryl groups or may be joined to form a ring compound. As is evident from the equation secondary alcoholis convertedto a ketone. Although this ketone can be rehydrogenated to the alcohol to obtain a continuous process, alternatively it may be preferred to utilize the ketone as such in other processes or for sale as a final product. A particular advantage of the use of hydrogen donors to supply hydrogen to the process is that this provides an efficient economical control of the amount of hydrogen added so as to obtain the selective hydrogenation desired. Thus, approximately stoichiometric amounts of the hydrogen transfer agent are used to obtain the saturation desired. Utilizing hydrogen donor reactants temperatures in the range of 100400 C. preferably l20-250 C. and pressures of from l20 atmospheres are preferred. It is also contemplated that mixtures of a hydrogen transfer agent and a separate displacing solvent may be used.
Where both hydrogen transfer agents and hydrogen are utilized temperatures will be in the range of 20400 C. and pressures will be in the range of l-lOO atmospheres.
An advantage for the use of both hydrogen transfer agents and gaseous hydrogen is that in case one does not want to continuously remove acetone when using isopropanol and at the same time maintain a high rate of hydrogenation, gaseous hydrogen can be added as soon as the hydrogen transfer rate becomes too slow form an economic standpoint.
The present invention will be more clearly understood from a consideration of the following examples which present data obtained in the laboratory.
Example 1 -was flushed with nitrogen, pressured to 300500 p.s.i.g.
withnitrogen and was heated, while being agitated, to the specified temperature for the specified time. In the cases where molecular hydrogen was used it was introduced intermittently to maintain pressure within the specified limits. Also, for comparison hydrogenation using PtO; as catalyst and gaseous hydrogen was also conducted.
u No 1 2 3 4 s 7 8 $011109 05 Hydrogen H2 H2 H3 H2 Cyclodo- Cyclo- Second- Isoprodecanol hexanol ary panol Butanol yst PtO Pro, Ni Ni d Ni d Ni Nl Ni Percent Catalyst z .2 .2 s 2 2 2 a 2 p ratur C 30-50 30-50 30-50 170 b 185 h 170 b 170 b 170 Pressure, p.s.i.g -50 20-50 20-50 f 1, 000 400 u 300 l 350 300 Length r11 1,hours 0.75 0. 75 4. 5 4. 5 5. 5 5. 0 3. 5 3. 5 rsi n. pcrcenL. 34 56 95 9s 99 88 96 72 Selectivity to: o
cy lodod cadiene 70 61 22 31 3 3s 7 45 y l d decene 22 29 56 63 88 02 so 52 Cycoldodecane 8 10 22 6 9 2 7 3 I Nitrogen pressure.
b Maximum temperature.
= Determined by mass spectra analysis.
5 Commercial Raney nickel dispersed in water. most cases by washing with the alcohol used as hydrogen donor.
6 Acetone used as displacing solvent.
1 Pressure at beginning of run. Dropped to zero at end of run.
2 Based on cyclododecatriene.
The data shown in the table clearly demonstrate the selective hydrogenation. With cyclodecanol and secondary butanol as hydrogen donors the selectivity to cyclododecene was 88 and 86% at conversion levels of 99 and 96% respectively. The selectivity to cyclododecane was less than 10% in either run. With isopropanol as hydrogen donor the conversion was only 72% due to the decrease in rate as a result of acetone buildup but as the data indicate the hydrogenation was selective. This is evident by comparing the selectivity to cyclododecene and cyclododecane in this run with the selectivities in the 56% conversion run using gaseous hydrogen and Pt0 as catalyst and the 95% conversion run (Run 3) using Raney nickel. That gaseous hydrogen can be employed in the presence of acetone is evident from Run 4. Thus it can be seen that selectivity using hydrogen in the presence of acetone is much better than that obtained in any of the hydrogenation only runs. Particularly, Run 3 shows poor selectivity due to the high level of cyclododecane obtained, i.e. 22% as compared to only 6% where an acetone displacement solvent is used.
What is claimed is:
1. The process for the selective hydrogenation of a C -C hydrocarbon more unsaturated than a monoolefin to an olefinic C -C hydrocarbon more saturated than the starting material which comprises reacting the more unsaturated hydrocarbon with at least the stoichiometric amount of a hydrogen source selected from the group consisting of C -C saturated aliphatic monohydric alcohols, C -C saturated cyclic monohydric alcohols, and mixtures of each of these materials with gaseous hydrogen to obtain hydrogenation to the desired olefinic material in the presence of a high surface area hydrogenation catalyst.
2. The process of claim 1 in which the hydrogen source is gaseous hydrogen and a C -C aliphatic secondary alcohol. 7
3. The process of claim 1 in which the hydrogen source is gaseous hydrogen and a C -C cyclic alcohol.
4. The process of claim 1 in which the starting material is a non-conjugated diolefin.
5. The process of claim 1 in which the starting material is cyclododecatriene and in which selective hydrogenation is conducted to produce preferentially cyclododecene. I
6. The process of claim 1 in which selective hydro- Water was removed by wash ing with acetone followed in the starting material which comprises reacting the more unsaturated hydrocarbon with at least the stoichiometric amount of a c3'-C12 alcohol hydrogen transfer agent selected from the group consisting of saturated aliphatic monohydric alcohols and saturated cyclic monohydric alcohols to obtain hydrogenation to the desired olefinic material in the presence of a high surface area hydrogenation catalyst.
8. The process of claim 7 in which the alcohol hydrogen transfer agent is a secondary alcohol.
9. The process of claim 7 in whichthe alcohol hydrogen transfer agent is a C -C secondary alcohol.
10. The process of claim 7 in which stoichiometric amounts of the alcohol to obtain the desired hydrogenation are utilized.
11. The process of claim 7 in which a diolefin is selectively hydrogenated to a monoolefin using stoichiometric amounts of the alcohol hydrogen transfer agent.
12. The process of claim 7 in which cyclododecatriene is selectively hydrogenated to cyclododecene utilizing stoichiometric amounts of cyclododecanol as the hydrogen transfer agent.
13. The process of claim 7 in which cyclododecatriene is selectively hydrogenated to cyclododecene utilizing gcnation is conducted at temperatures of 20-400" C. and
stoichiometric amounts of cyclohexanol as a hydrogen transfer agent.
14. The process of claim 7 in which cyclododecatriene is selectively hydrogenated to cyclododecene utilizing stoichiometric amounts of secondary butanol as the hydrogen transfer agent.
15. The process of claim 7 in which cyclododecatriene is selectively hydrogenated to cyclododecene utilizing stoichiometric amounts of isopropanol as the hydrogen transfer. agent.
16. The process of claim 7 in which cyclododecatriene is selectively hydrogenated to cyclododecene utilizing stoichiometric amounts of a C -C secondary alcohol as the hydrogen transfer agent.
17. The process of claim 7 in which the alcohol hydrogen transfer agent is a cyclic alcohol.
18. The process of claim 7 in which selective hydrogenation is conducted at'temperatures of 20400 C. and pressures of from 1-100 atmospheres and in which stoichiometric amounts of the hydrogen transfer agent to obtain the desired hydrogenation are utilized.
References Cited in the file 'of this patent UNITED STATES PATENTS
Claims (1)
1. THE PROCESS FOR THE SELECTIVE HYDROGENATION OF A C3-C24 HYDROCARBON MORE UNSATURATED THAN A MONOOLEFIN TO AN OLEFINIC C3-C24 HYDROCARBON MORE SATURATED THAN THE STARTING MATERIAL WHICH COMPRISES REACTING THE MORE UNSATURATED HYDROCARBON WITH AT LEAST THE STOICHIOMETRIC AMOUNT OF A HYDROGEN SOURCE SELECTED FROM THE GROUP CONSISTING OF C3-C12 SATURATED ALIPHATIC MONOHYDRIC ALCOHOLS, C3-C12 SATURATED CYCLIC MONOHYDRIC ALCOHOLS, AND MIXTURES OF EACH OF THESE MATERIALS WITH GASEOUS HYDROGEN TO OBTAIN HYDROGENATION TO THE DESIRED OLEFINIC MATERIAL IN THE PRESENCE OF A HIGH SURFACE AREA HYDROGENATION CATALYST.
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| US804606A US3022359A (en) | 1959-04-07 | 1959-04-07 | Selective hydrogenation of cyclododecatriene to cyclododecene |
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| US804606A US3022359A (en) | 1959-04-07 | 1959-04-07 | Selective hydrogenation of cyclododecatriene to cyclododecene |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3127452A (en) * | 1961-06-07 | 1964-03-31 | It Resine Soc | Method of hydrogenating alphamethylstyrene to cumene |
| US3182093A (en) * | 1961-10-02 | 1965-05-04 | Exxon Research Engineering Co | Preparation of 1, 5-cyclododecadiene |
| US3294853A (en) * | 1965-02-04 | 1966-12-27 | Universal Oil Prod Co | Selective hydrogenation of trans, cis-1, 5-cyclodecadiene to cis-cyclodecene |
| US3316319A (en) * | 1964-06-04 | 1967-04-25 | Du Pont | Polyolefinic selective hydrogenation |
| US3324189A (en) * | 1964-03-24 | 1967-06-06 | Huels Chemische Werke Ag | Process for the purification of the waste gases from the liquid-phase oxidation of cyclododecane |
| US3342884A (en) * | 1965-11-18 | 1967-09-19 | Phillips Petroleum Co | Novel cyclohexyl derivatives of ethylene and methods for their preparation |
| US3360577A (en) * | 1963-04-18 | 1967-12-26 | Geigy Ag J R | Selective hydrogenation |
| US3369052A (en) * | 1963-10-29 | 1968-02-13 | Geigy Chem Corp | Production of cyclic alkene |
| US3400166A (en) * | 1966-12-21 | 1968-09-03 | Columbian Carbon | Selective hydrogenation of cyclododecatriene |
| US3400164A (en) * | 1966-07-05 | 1968-09-03 | Columbian Carbon | Selective hydrogenation of cyclododecatriene to cyclododecene |
| US3400165A (en) * | 1966-07-05 | 1968-09-03 | Columbian Carbon | Selective hydrogenation of cyclododecatriene |
| US3418386A (en) * | 1966-07-05 | 1968-12-24 | Columbian Carbon | Hydrogenation of cyclooctadienes to cyclooctenes |
| US3472906A (en) * | 1965-06-29 | 1969-10-14 | Lever Brothers Ltd | Hydrogenation process |
| US3493625A (en) * | 1965-12-10 | 1970-02-03 | Phillips Petroleum Co | Selective hydrogenation of cyclic polyenes |
| US3499050A (en) * | 1968-08-12 | 1970-03-03 | Du Pont | Hydrogenation of cyclododecatriene to cyclododecene |
| US3513210A (en) * | 1969-02-24 | 1970-05-19 | Du Pont | Hydrogenation of cyclododecatriene |
| US3862252A (en) * | 1972-12-28 | 1975-01-21 | Kanegafuchi Chemical Ind | Method of selective hydrogenation of cyclopentadiene |
| US4108911A (en) * | 1977-11-11 | 1978-08-22 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene to form cyclopentene using Raney nickel catalyst and polyol reactant |
| US4112007A (en) * | 1975-05-23 | 1978-09-05 | Anic S.P.A. | Selective hydrogenation in gaseous phase of cyclopentadiene or a mixture of ethylene and acetylene using a palladium zinc catalyst deactivated with ammonia, ammonium chloride, steam, or their mixtures |
| US4162271A (en) * | 1977-11-11 | 1979-07-24 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene to form cyclopentene using Raney nickel catalyst and alcohols boiling above 95° C. in the reaction mixture |
| US4204081A (en) * | 1978-08-30 | 1980-05-20 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene to form cyclopentene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2204978A (en) * | 1939-04-04 | 1940-06-18 | Du Pont | Method for producing cyclohexane and acetone |
| US2360555A (en) * | 1942-03-17 | 1944-10-17 | Shell Dev | Preparation of cyclic mono-olefins |
| US2686208A (en) * | 1950-09-12 | 1954-08-10 | Ici Ltd | Production of cyclo-olefinic compounds |
| US2686209A (en) * | 1951-11-19 | 1954-08-10 | Ici Ltd | Production of cyclo-olefinic compounds |
| US2887517A (en) * | 1953-06-29 | 1959-05-19 | Ruhrchemie Ag | Production of cyclopentene |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3127452A (en) * | 1961-06-07 | 1964-03-31 | It Resine Soc | Method of hydrogenating alphamethylstyrene to cumene |
| US3182093A (en) * | 1961-10-02 | 1965-05-04 | Exxon Research Engineering Co | Preparation of 1, 5-cyclododecadiene |
| US3360577A (en) * | 1963-04-18 | 1967-12-26 | Geigy Ag J R | Selective hydrogenation |
| US3369052A (en) * | 1963-10-29 | 1968-02-13 | Geigy Chem Corp | Production of cyclic alkene |
| US3324189A (en) * | 1964-03-24 | 1967-06-06 | Huels Chemische Werke Ag | Process for the purification of the waste gases from the liquid-phase oxidation of cyclododecane |
| DE1277852B (en) * | 1964-06-04 | 1968-09-19 | Du Pont | Process for the preparation of C- to C-cycloalkenes with a ring by selective hydrogenation of the corresponding non-conjugated polyolefins over a palladium catalyst |
| US3316319A (en) * | 1964-06-04 | 1967-04-25 | Du Pont | Polyolefinic selective hydrogenation |
| US3294853A (en) * | 1965-02-04 | 1966-12-27 | Universal Oil Prod Co | Selective hydrogenation of trans, cis-1, 5-cyclodecadiene to cis-cyclodecene |
| US3472906A (en) * | 1965-06-29 | 1969-10-14 | Lever Brothers Ltd | Hydrogenation process |
| US3342884A (en) * | 1965-11-18 | 1967-09-19 | Phillips Petroleum Co | Novel cyclohexyl derivatives of ethylene and methods for their preparation |
| US3493625A (en) * | 1965-12-10 | 1970-02-03 | Phillips Petroleum Co | Selective hydrogenation of cyclic polyenes |
| US3400165A (en) * | 1966-07-05 | 1968-09-03 | Columbian Carbon | Selective hydrogenation of cyclododecatriene |
| US3418386A (en) * | 1966-07-05 | 1968-12-24 | Columbian Carbon | Hydrogenation of cyclooctadienes to cyclooctenes |
| US3400164A (en) * | 1966-07-05 | 1968-09-03 | Columbian Carbon | Selective hydrogenation of cyclododecatriene to cyclododecene |
| US3400166A (en) * | 1966-12-21 | 1968-09-03 | Columbian Carbon | Selective hydrogenation of cyclododecatriene |
| US3499050A (en) * | 1968-08-12 | 1970-03-03 | Du Pont | Hydrogenation of cyclododecatriene to cyclododecene |
| US3513210A (en) * | 1969-02-24 | 1970-05-19 | Du Pont | Hydrogenation of cyclododecatriene |
| US3862252A (en) * | 1972-12-28 | 1975-01-21 | Kanegafuchi Chemical Ind | Method of selective hydrogenation of cyclopentadiene |
| US4112007A (en) * | 1975-05-23 | 1978-09-05 | Anic S.P.A. | Selective hydrogenation in gaseous phase of cyclopentadiene or a mixture of ethylene and acetylene using a palladium zinc catalyst deactivated with ammonia, ammonium chloride, steam, or their mixtures |
| US4108911A (en) * | 1977-11-11 | 1978-08-22 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene to form cyclopentene using Raney nickel catalyst and polyol reactant |
| US4162271A (en) * | 1977-11-11 | 1979-07-24 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene to form cyclopentene using Raney nickel catalyst and alcohols boiling above 95° C. in the reaction mixture |
| US4204081A (en) * | 1978-08-30 | 1980-05-20 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene to form cyclopentene |
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