US1938177A - Preparation of secondary alcohols - Google Patents
Preparation of secondary alcohols Download PDFInfo
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- US1938177A US1938177A US1938177DA US1938177A US 1938177 A US1938177 A US 1938177A US 1938177D A US1938177D A US 1938177DA US 1938177 A US1938177 A US 1938177A
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- olefines
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- 150000003333 secondary alcohols Chemical class 0.000 title description 22
- 238000002360 preparation method Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 description 47
- 239000007788 liquid Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 26
- 229930195733 hydrocarbon Natural products 0.000 description 25
- 150000002430 hydrocarbons Chemical class 0.000 description 25
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 18
- 230000000379 polymerizing effect Effects 0.000 description 18
- 230000032050 esterification Effects 0.000 description 17
- 238000005886 esterification reaction Methods 0.000 description 17
- 150000002148 esters Chemical class 0.000 description 15
- 230000003301 hydrolyzing effect Effects 0.000 description 13
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZTHQBROSBNNGPU-UHFFFAOYSA-N Butyl hydrogen sulfate Chemical compound CCCCOS(O)(=O)=O ZTHQBROSBNNGPU-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- -1 tri-isobutylene hydrogen sulfate Chemical compound 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KOYGZROXUOTUEE-UHFFFAOYSA-N butane;but-1-ene Chemical compound CCCC.CCC=C KOYGZROXUOTUEE-UHFFFAOYSA-N 0.000 description 3
- 150000001722 carbon compounds Chemical class 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LMEDOLJKVASKTP-UHFFFAOYSA-N dibutyl sulfate Chemical compound CCCCOS(=O)(=O)OCCCC LMEDOLJKVASKTP-UHFFFAOYSA-N 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
-
- 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
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
- C07C29/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis
- C07C29/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis the acid being sulfuric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/17—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with acids or sulfur oxides
- C07C7/171—Sulfuric acid or oleum
Definitions
- This invention relates to a process for the preparation of secondary alcohols from olefinic mixtures and is more particularly concerned with a process wherein highly reactive olefines are 5 rendered relatively inactive prior to the esterification of the less reactive olefines present without substantially sacrificing the yield of the latter reaction product.
- the strength of acid employed was in the nature of a compromise; it was strong enough at the particular operating temperature to completely polymerize the highly reactive unsaturates, such as dioleflnes and tertiary-base olefines (olefines capable of yielding tertiary alcohols upon hydrolysis) without permitting such a rapid and excessive rise in temperature as to cause the substantial polymerization of the less reactive unsaturates such as secondary-base olefines (o lefines capable of yielding secondary alcohols upon hydrolysis). Accordingly, theacid was never strong enough at the particular operating temperature to convert substantially all of the secondary-base olefines to theircorresponding esters. The yield of the latter'wassacrificed due to thermal conditions.
- the preferred initial material is substantially stripped of hydrocarbons containing less than four carbon atoms to the molecule and suitably 0 fractionated into fractions containing hydrocarbons of the same number of carbon atoms to the molecule. In certain instances, it will be difiicult to remove traces of higher and lower carbon compounds, but their presence is not detrimental to our process. In certain other situations, it may be desirable to operate with a fraction containing a mixture of carbon compounds-such as a 4 and 5 carbon compound fraction. We prefer to practice our process with a substantially pure fraction of hydrocarbons of which each molecule contains the same number of carbon atoms to the molecule.
- the desired fraction in the liquid state is contacted with the polymerizing agent in any suitable manner, with or without pressure.
- resort may be hadto the agitation of the of throughput of the olefine-containing fluid.
- the rate of throughput and the strength of acid employed are adjusted according to the character and quantity of the tertiary-base olefine and the temperature of the process so that negligible esterification andpolymerization of secondary-base olefines occur.
- the rate of through-' put of the butane-butene fraction is about 0.6 gallons/minute/gallon reaction space when the isobutylene content is about 18% by weight employing 70% H2804.
- the acid under the above conditions is 0.3 gallons/minute/gallon reaction space.
- the reaction temperature is maintained in the above example at 122 F. and it has been found necessary to supply heat to the reaction. It is to be understood that as stronger acids are employed, the rates of throughput of the reactants are either decreased or the reaction temperature maintained below 122 F. The converse is true with weaker acids.
- the isobutylene polymerizes under the conditions of the process whereas butene-1 and butene-2 substantially. do not and the former is associated with the butane and isobutane (parafin hydrocarbons), if any is present. Any dioleflne present in the fraction undergoing treatment is polymerized practically simultaneousl with the is'obutylene.
- the fluid containing polymers and free secondary butene as well as butane and possibly isobutane is introduced into a'reactor wherein it is contacted with 90% to 100% H2SO4 at a tempera-
- the reaction progresses in the direction of butyl hydrogen sulfate.
- the liquid mixture in the vessel separates into two liquid phases, the upper layer comprising essentially butane and the lower layer butyl hydrogen sulfate. Any dibutyl sulfate, if formed, is found dissolved in both layers.
- the isobutylene polymers will collect with the butane.
- the lower layer is separated from the upper layer by any convenient mode and is then hydrolyzed with an aqueous medium such as water, aqueous alcohol, preferably secondary alcohol, and the like so that the diluted liquid has an acidity of 10% to 15%.
- the amount of dibutyl sulfate in the lower layer is quite small and forms a layer on the surface of the dilute acid product which layer is removed in any suitable manner and subsequently converted to secondary butyl alcohol as by dis- I tillation with weak acid, aqueous or acid solutions of alcohols, preferably of secondary alcohols, alkyl hydrogen sulfate solution or with water (either in the presence or absence of a suitable emulsifying agent) Any di-or tri-isobutylene hydrogen sulfate, if formed earlier in the process, will revert back to the original polymer or some higher polymer and can be easily separated from the butyl hydrogen sulfate due to the differences in specific gravity.
- the dior tri-isobutylene hydrogen sulfate may form a certain amount of alcohol on dilution which will be retained in the acid solution of butyl hydrogen sulfate. This is not detrimental in view of the following:
- the acid solution is diluted to an acidity of about 15% and heated to liberate the secondary butyl alcohol
- W 2.A. method of producing secondary alcohols from a mixture of olefines in the liquid state, comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary-base olefines, treating the resulting liquid mixture with H2804 of a strength and at a temperature at which substantial esterification of the secondary-base olefines is-effected and hydrolyzing the resulting esters.
- a method of producing secondary alcohols from a mixture of olefines in the liquid state comprising: polymerizing tertiary-base olefines,
- a method of producing secondary alcohols from a mixture of olefines in the liquid state comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary-base olefines, treating the resulting mixture with H2804 of a strength and at a temperature at which substantial esterification of the secondary-base olefines is effected, removing the polymers from the esters formed and hydrolyzing the latter.
- a method of producing secondary alcohols from a mixture of olefine and. paraflin hydrocarbons in the liquid state comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondarybase olefines, treating the resulting liquid mixture with a polybasic inorganic acid of a strength and at a temperature at which substantial esterification of the secondary-base olefines is effected, separating the esters formed from the mixture and hydrolyzing the former.
- a method of producing secondary alcohols from a mixture of olefine and parafiin hydrocarbons in the liquid state comprising: polymerizfrom a mixture of olefine and paraffin hydrocarbons in the liquid state, comprising: polymerizing tertiary-base olefines, which 'are present, without the substantial conversion ofsecondarybase olefines, treating the resultingliquid mixture with about 90% to about 100% 1-1250; at a temperature at which substantial esterification of the secondary-base olefines is efiected, separating the esters formed from the mixture and hydrolyzing the former.
- a method of producing secondary alcohols from a liquid hydrocarbon fraction which contains olefine hydrocarbons containing more than three carbon atoms to the molecule comprising: polymerizing tertiary-base olefines, which are present, without thesubstantial conversion of secondary-base olefines, treating the resulting liquid mixturewith a polybasic inorganic acid of a strength and at a temperature at which substantial esterification of the secondary-base olefines is efiected, separating the esters formed from the mixture and hydrolyzing the former.
- a method of producing secondary alcohols I from a liquid hydrocarbon fraction which contains olefine hydrocarbons containing more than three carbon atoms to the molecule comprising? polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary-base olefines, treating the resulting liquid mixture with H2504 of a strength and at a temperature at which substantial esterification of the secondary-base olefinesiseffected,separating the esters formed from the mixture and by:
- a method of producing secondary alcohols from a liquid hydrocarbon fraction which contains olefine hydrocarbons containing more than three carbon atoms to the molecule comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary-base olefines, treating the resulting liquid mixture with about to about 100% H2804 at a temperature at which substantial esterification of the secondary-base olefines is effected, separating the esters formed from the mixture and hydrolyzing the former.
- a method of producing secondary butanol from liquid hydrocarbon mixtures containing butylene and isobutylene comprising: polymerizing the isobutylene without the substantial conversion of the butylene, treating the. resulting liquid mixture with a polybasic inorganic acid of a strength and at a temperature at which substantial esterification of the butylene is efiected, separating the esters formed from the mixture and hydrolyzing the former.
- a method of producing secondary butanol from liquid hydrocarbon mixtures containing butylene and isobutylene comprising: polymerizing the isobutylene without the substantial conversion of the butylene, treating'theresulting liquid mixture with H2804 of a strength and at a temperature at which substantial esterificationof the butylene is effected, separating the esters formed from the mixture and hydrolyzing the former.
- a method of producing secondary butanol from liquid hydrocarbon mixtures containing butylene and isobutylene comprising: polymerizing the isobutylene without the substantial conversion of the butylene, treating the resulting liquid mixture with about 90% to about 100% H2804 at a temperature at which substantial esterification of the butylene is effected, separating the esters formed from the mixture. and hydrolyzing the former.
- a method of producing secondary pentanol from liquid hydrocarbon mixtures containing 'amylene and trimethyl ethylene comprising: polymerizing the trimethyl ethylene without the substantial conversion of the 'amylene, treating the resulting liquid mixture with a polybasic in- 16.
- a method of producing secondary pentanol from liquid hydrocarbon mixtures containing amylene and trimethyl ethylene comprising: polymerizingthe trimethyl ethylene without the substantial conversion of the amylene, treating the resulting liquid mixture with H2804 of a strength and at a temperature at which substantial esteriflcation of the amylene is effected, separating the esters formed from the mixture and hydrolyzing the former.
- a niethod of producing secondary pentanol from liquid hydrocarbon mixtures containing amylene and trimethyl ethylene comprising: polymerizing the trimethyl ethylene without the substantial conversion of the amylene, treating the resulting liquid mixture with about 90% to about 100% H2804 at a temperature at which substantial esterification of the amylene is effected, separating the esters formed from the mixture and hydrolyzing the former.
- a method of producing secondary alcohols from a mixture of olefines in the liquid state comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary base olefines, and treating the resulting liquid mixture with a polybasic inorganic acid of a strength and at a temperature at which substantial esteri-fication of the secondary base olefines is effected.
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Description
V Patented Dec. 5, 1933 PREPARATION OF SECONDARY ALCOHOLS William Engs and Richard Z. Moravec, Berkeley,
Caliii, assignors to Shell Development Company, SanFrancisco, Calif., a corporation of Delaware No Drawing.
Application August 31, 1931 Serial No. 560,508
Claims- (Cl. 260-456) This invention relates to a process for the preparation of secondary alcohols from olefinic mixtures and is more particularly concerned with a process wherein highly reactive olefines are 5 rendered relatively inactive prior to the esterification of the less reactive olefines present without substantially sacrificing the yield of the latter reaction product.
Prior investigators have utilized olefine-conm taining fluids, such as those derived by the pyrogenetic treatment of peat, coal, oil shales and like carboniferous natural-materials to produce secondary alcohols but very few have been concerned with the proper treatment of highly re- 315' active unsaturates prior to the formation of the desirable secondary alcohols. Earlier workers have either employed an acid of. such strength and under predetermined conditions that the highly reactive unsaturates have been completegg ly polymerized while the less reactive unsaturates have been only partly esterified, thus decreasing the possible effective yield of secondary alcohol upon hydrolysis or have first polymerized and removed the highly reactive unsaturates prior to the esteriflcation of 'the less reactive unsaturates. In the first situation, the strength of acid employed was in the nature of a compromise; it was strong enough at the particular operating temperature to completely polymerize the highly reactive unsaturates, such as dioleflnes and tertiary-base olefines (olefines capable of yielding tertiary alcohols upon hydrolysis) without permitting such a rapid and excessive rise in temperature as to cause the substantial polymerization of the less reactive unsaturates such as secondary-base olefines (o lefines capable of yielding secondary alcohols upon hydrolysis). Accordingly, theacid was never strong enough at the particular operating temperature to convert substantially all of the secondary-base olefines to theircorresponding esters. The yield of the latter'wassacrificed due to thermal conditions. In the second situation, resort was had to the removal of the poly- 5 merized highly reactive unsaturates prior to the esterification of the secondary-base olefines as it was believed that otherwise the process could not be successfully operated, thus necessitating an operation which is dispensed with in our process. U
We have discovered that secondary alcohols can be prepared simply and economically from olefine-containing fiuids of the type mentioned heretofore by properly controlling the polymerization of the highly reactive unsaturates and subsequently esterifying the secondary-base olefines in the presence of the polymers.
The preferred initial material is substantially stripped of hydrocarbons containing less than four carbon atoms to the molecule and suitably 0 fractionated into fractions containing hydrocarbons of the same number of carbon atoms to the molecule. In certain instances, it will be difiicult to remove traces of higher and lower carbon compounds, but their presence is not detrimental to our process. In certain other situations, it may be desirable to operate with a fraction containing a mixture of carbon compounds-such as a 4 and 5 carbon compound fraction. We prefer to practice our process with a substantially pure fraction of hydrocarbons of which each molecule contains the same number of carbon atoms to the molecule. In segregating the hydrocarbons into suitable fractions, it will be found practically impossible to separate the parafiin hydrocarbons from the olefine hydrocarbons possessing the same number of carbon atoms to the molecule without uneconomical and complicated procedures. As the paraffin hydrocarbons may be considered as inert compounds in our process, their presence in their corresponding carbon compound fraction is not accompanied by any detrimental effect.
' 'Ifhe fractions to be treated are thus characteristically composed of paraffin hydrocarbons, s5 olefines, both iscand normal, which yield secondary derivatives (hereinafter designated as secondary-base olefines), iso-olefines which yield tertiary derivatives (hereinafter designated as tertiary-base olefines) and traces of diolefines such as butadiene and isoprene.
For illustrative purposes only, reference will be had to a substantially pure B-B fraction which represents a mixture of butane and butene obtained by, distillation or condensation or both.
' Besides the butane there will be normally present organic acids as benzene sulfonic acids or the sulfonic acids of the homologues of benzene.
The desired fraction in the liquid state is contacted with the polymerizing agent in any suitable manner, with or without pressure. For example, resort may be hadto the agitation of the of throughput of the olefine-containing fluid.
With'stronger acids, lower temperatures in the reactor must prevail and/or the rate of throughput should be greater whereas with relatively weak acids, higher temperatures may be maintained in the reactor with or without a decreased rate of throughput. The rate of throughput and the strength of acid employed are adjusted according to the character and quantity of the tertiary-base olefine and the temperature of the process so that negligible esterification andpolymerization of secondary-base olefines occur. In practicing our invention, we preferably employ 60% to 70% HzSO-i as it apparently yields the best results with butane-butene and pentanepentene fractions, which contain secondary amylenes, trimethyl ethylene and/or other tertiary amylene, or the like. The rate of through-' put of the butane-butene fraction is about 0.6 gallons/minute/gallon reaction space when the isobutylene content is about 18% by weight employing 70% H2804. the acid under the above conditions is 0.3 gallons/minute/gallon reaction space. The reaction temperature is maintained in the above example at 122 F. and it has been found necessary to supply heat to the reaction. It is to be understood that as stronger acids are employed, the rates of throughput of the reactants are either decreased or the reaction temperature maintained below 122 F. The converse is true with weaker acids. With fractions containing hydrocarbons containing different numbers of carbon atoms to the molecule, the heavier molecular fractions are more sensitive to the action of acid and consequently the conditions preferable with a butane-butene fraction are too strenuous for a pentane-pentene fraction and modifications apparent to the chemist are necessary.
The isobutylene polymerizes under the conditions of the process whereas butene-1 and butene-2 substantially. do not and the former is associated with the butane and isobutane (parafin hydrocarbons), if any is present. Any dioleflne present in the fraction undergoing treatment is polymerized practically simultaneousl with the is'obutylene.
In certain instances, as above, an input of heat is necessary to maintain the proper reaction temperature although with stronger acids and/or slower rates of throughput, the reactants may be brought together without any external application of heat due to the exothermic heat of reaction. In the latter situation no cooling is necessary during the polymerization stage as the potential temperature rise above the maximum re action temperature may be compensated for by adjustment of the rate of throughput of the olefine-containing fluid and/or acid. 7
The fluid containing polymers and free secondary butene as well as butane and possibly isobutane is introduced into a'reactor wherein it is contacted with 90% to 100% H2SO4 at a tempera- The rate of throughput of haps a dior tri-isobutylene hydrogen sulfate but this may be taken 'care of by maintaining a slight excess of acid in the second reactor.
Where substantially one molecule of acid has been employed for each molecule of butene, the reaction progresses in the direction of butyl hydrogen sulfate. The liquid mixture in the vessel separates into two liquid phases, the upper layer comprising essentially butane and the lower layer butyl hydrogen sulfate. Any dibutyl sulfate, if formed, is found dissolved in both layers. The isobutylene polymers will collect with the butane. The lower layer is separated from the upper layer by any convenient mode and is then hydrolyzed with an aqueous medium such as water, aqueous alcohol, preferably secondary alcohol, and the like so that the diluted liquid has an acidity of 10% to 15%. The amount of dibutyl sulfate in the lower layer is quite small and forms a layer on the surface of the dilute acid product which layer is removed in any suitable manner and subsequently converted to secondary butyl alcohol as by dis- I tillation with weak acid, aqueous or acid solutions of alcohols, preferably of secondary alcohols, alkyl hydrogen sulfate solution or with water (either in the presence or absence of a suitable emulsifying agent) Any di-or tri-isobutylene hydrogen sulfate, if formed earlier in the process, will revert back to the original polymer or some higher polymer and can be easily separated from the butyl hydrogen sulfate due to the differences in specific gravity. The dior tri-isobutylene hydrogen sulfate may form a certain amount of alcohol on dilution which will be retained in the acid solution of butyl hydrogen sulfate. This is not detrimental in view of the following: The acid solution is diluted to an acidity of about 15% and heated to liberate the secondary butyl alcohol While we have in the foregoing described insome detailthe preferred embodiment of our invention and some variants thereof, it will be understood that this is only for the purpose of making the invention more clear and that the invention is not to be regarded as limited to the details of operation described, nor is it dependent upon the soundness or accuracy of the theories which we have advanced as to the reasons for the advantageous results attained. On the other hand, the invention is toibe regarded as limited only by the terms of the accompanying claims, in which it is our intention to claim all novelty inherent therein as broadly as is possible. in view of the prior art.
We claim as our invention:
1. A method of producing secondary alcohols from a mixture of olefines in the liquid state,
comprising: polymerizing tertiary hase olefines, which are present, without the substantial conversion of secondary-base olefines,'treating the resulting liquid mixture with a polybasic inorganic acid of a strength and at a temperature at which substantial esterification of the secondary base olefines is efi'ected and hydrolyzing the resulting esters. W 2.A.,method of producing secondary alcohols from a mixture of olefines in the liquid state, comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary-base olefines, treating the resulting liquid mixture with H2804 of a strength and at a temperature at which substantial esterification of the secondary-base olefines is-effected and hydrolyzing the resulting esters.
4. A method of producing secondary alcohols from a mixture of olefines in the liquid state, comprising: polymerizing tertiary-base olefines,
I which are present, without the substantial conversion of secondary-base olefines, treating the resulting liquid mixture with a polybasic inorganic acid of a strength and at a temperature at which substantial esterification of the secondarybase olefines is effected, removing the polymers from the esters formed and hydrolyzing the latter.
'5. A method of producing secondary alcohols from a mixture of olefines in the liquid state, comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary-base olefines, treating the resulting mixture with H2804 of a strength and at a temperature at which substantial esterification of the secondary-base olefines is effected, removing the polymers from the esters formed and hydrolyzing the latter.
6. A method of producing secondary alcohols from a mixture of olefine and. paraflin hydrocarbons in the liquid state, comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondarybase olefines, treating the resulting liquid mixture with a polybasic inorganic acid of a strength and at a temperature at which substantial esterification of the secondary-base olefines is effected, separating the esters formed from the mixture and hydrolyzing the former.
7. A method of producing secondary alcohols from a mixture of olefine and parafiin hydrocarbons in the liquid state, comprising: polymerizfrom a mixture of olefine and paraffin hydrocarbons in the liquid state, comprising: polymerizing tertiary-base olefines, which 'are present, without the substantial conversion ofsecondarybase olefines, treating the resultingliquid mixture with about 90% to about 100% 1-1250; at a temperature at which substantial esterification of the secondary-base olefines is efiected, separating the esters formed from the mixture and hydrolyzing the former.
9. A method of producing secondary alcohols from a liquid hydrocarbon fraction which contains olefine hydrocarbons containing more than three carbon atoms to the molecule, comprising: polymerizing tertiary-base olefines, which are present, without thesubstantial conversion of secondary-base olefines, treating the resulting liquid mixturewith a polybasic inorganic acid of a strength and at a temperature at which substantial esterification of the secondary-base olefines is efiected, separating the esters formed from the mixture and hydrolyzing the former.
10. A method of producing secondary alcohols I from a liquid hydrocarbon fraction which contains olefine hydrocarbons containing more than three carbon atoms to the molecule, comprising? polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary-base olefines, treating the resulting liquid mixture with H2504 of a strength and at a temperature at which substantial esterification of the secondary-base olefinesiseffected,separating the esters formed from the mixture and by:
drolyzing the former.
11. A method of producing secondary alcohols from a liquid hydrocarbon fraction which contains olefine hydrocarbons containing more than three carbon atoms to the molecule, comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary-base olefines, treating the resulting liquid mixture with about to about 100% H2804 at a temperature at which substantial esterification of the secondary-base olefines is effected, separating the esters formed from the mixture and hydrolyzing the former.
12. A method of producing secondary butanol from liquid hydrocarbon mixtures containing butylene and isobutylene, comprising: polymerizing the isobutylene without the substantial conversion of the butylene, treating the. resulting liquid mixture with a polybasic inorganic acid of a strength and at a temperature at which substantial esterification of the butylene is efiected, separating the esters formed from the mixture and hydrolyzing the former.
13. A method of producing secondary butanol from liquid hydrocarbon mixtures containing butylene and isobutylene, comprising: polymerizing the isobutylene without the substantial conversion of the butylene, treating'theresulting liquid mixture with H2804 of a strength and at a temperature at which substantial esterificationof the butylene is effected, separating the esters formed from the mixture and hydrolyzing the former.
14. A method of producing secondary butanol from liquid hydrocarbon mixtures containing butylene and isobutylene, comprising: polymerizing the isobutylene without the substantial conversion of the butylene, treating the resulting liquid mixture with about 90% to about 100% H2804 at a temperature at which substantial esterification of the butylene is effected, separating the esters formed from the mixture. and hydrolyzing the former.
1-5. A method of producing secondary pentanol from liquid hydrocarbon mixtures containing 'amylene and trimethyl ethylene, comprising: polymerizing the trimethyl ethylene without the substantial conversion of the 'amylene, treating the resulting liquid mixture with a polybasic in- 16. A method of producing secondary pentanol from liquid hydrocarbon mixtures containing amylene and trimethyl ethylene, comprising: polymerizingthe trimethyl ethylene without the substantial conversion of the amylene, treating the resulting liquid mixture with H2804 of a strength and at a temperature at which substantial esteriflcation of the amylene is effected, separating the esters formed from the mixture and hydrolyzing the former.
17. A niethod of producing secondary pentanol from liquid hydrocarbon mixtures containing amylene and trimethyl ethylene, comprising: polymerizing the trimethyl ethylene without the substantial conversion of the amylene, treating the resulting liquid mixture with about 90% to about 100% H2804 at a temperature at which substantial esterification of the amylene is effected, separating the esters formed from the mixture and hydrolyzing the former.
18. In a method of producing secondary alcohols from a mixture of olefines in the liquid state, the steps comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary base olefines, and
treating the resulting liquid mixture with an in-- organic acid of a strength and at a temperature 'at which substantial esterification of the secondary base olefines is effected.
19. In a method of producing secondary alcohols from a mixture of olefines in the liquid state, the steps comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary base olefines, and treating the resulting liquid mixture with a polybasic inorganic acid of a strength and at a temperature at which substantial esteri-fication of the secondary base olefines is effected.
20. In a method'of producing secondary alcohols from a mixture of olefines in the liquid state, the steps comprising: polymerizing tertiary-base olefines, which are present, without the substantial conversion of secondary base olefines, and treating the resulting liquid mixture with H2804 of a strength and at a temperature at which substantial esteriflcation of the secondary base olefines is efiected.
WILLIAM ENGS. RICHARD Z. MORAVEC.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1938177A true US1938177A (en) | 1933-12-05 |
Family
ID=3425964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US1938177D Expired - Lifetime US1938177A (en) | Preparation of secondary alcohols |
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| Country | Link |
|---|---|
| US (1) | US1938177A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2496251A (en) * | 1950-01-31 | Alcohol process | ||
| US2543820A (en) * | 1945-12-22 | 1951-03-06 | Standard Oil Dev Co | Alcohol process |
-
0
- US US1938177D patent/US1938177A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2496251A (en) * | 1950-01-31 | Alcohol process | ||
| US2543820A (en) * | 1945-12-22 | 1951-03-06 | Standard Oil Dev Co | Alcohol process |
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