US2007159A - Segregation of tertiary base olefines - Google Patents
Segregation of tertiary base olefines Download PDFInfo
- Publication number
- US2007159A US2007159A US541526A US54152631A US2007159A US 2007159 A US2007159 A US 2007159A US 541526 A US541526 A US 541526A US 54152631 A US54152631 A US 54152631A US 2007159 A US2007159 A US 2007159A
- Authority
- US
- United States
- Prior art keywords
- tertiary
- base
- acid
- olefine
- olefines
- 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 - Lifetime
Links
- 238000005204 segregation Methods 0.000 title description 2
- 229930195733 hydrocarbon Natural products 0.000 description 95
- 150000002430 hydrocarbons Chemical class 0.000 description 95
- 239000000203 mixture Substances 0.000 description 89
- 239000004215 Carbon black (E152) Substances 0.000 description 66
- 239000002253 acid Substances 0.000 description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 43
- 229920000642 polymer Polymers 0.000 description 31
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 27
- 239000002250 absorbent Substances 0.000 description 23
- 230000002745 absorbent Effects 0.000 description 23
- 238000004064 recycling Methods 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 238000010924 continuous production Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000000926 separation method Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- 230000000379 polymerizing effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 238000005336 cracking Methods 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 8
- 239000012188 paraffin wax Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 150000001722 carbon compounds Chemical class 0.000 description 4
- 150000003333 secondary alcohols Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- -1 butene-l Chemical compound 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000915 furnace ionisation nonthermal excitation spectrometry Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 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
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BALXUFOVQVENIU-KXNXZCPBSA-N pseudoephedrine hydrochloride Chemical group [H+].[Cl-].CN[C@@H](C)[C@@H](O)C1=CC=CC=C1 BALXUFOVQVENIU-KXNXZCPBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003460 sulfonic acids 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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
Definitions
- This invention relates to a process for the segregation of highly reactive olefines from olefinic mixtures containing more than three carbon atoms and ismore particularly concernedwith a continuous cyclic process which effects an economy in the necessary amount of selective solvent required to selectively absorb the highly reactive
- secondary alcohols can be prepared' simply and economically from olefine-containing gases of the type mentioned heretofore by practicing the selective removal of highly reactive olefines in a continuous manner wherein the selective absorbent is continuously recovered and recyc ed for further use.
- the preferred mm 1 material is substantially stripped of hydrocar ons containing less than four carbonatoms and suitably fractionated into fractions containing hydrocarbons of the same number ofcarbon atoms. In certain instances,
- fractions to be treated are thus characteristically composed of paraffin hydrocarbons, olefines, both iso-- "and normal, which yield secondary derivatives (hereinafter designated as secondary-base olefines), iso-olefines which yield phosphoric .acid are typical).
- tertiary-base-olefines tertiary-base-olefines
- traces of diolefines such as butadiene and isoprene.
- the desired fraction either in the gaseous or liquidstate--the liquid state promoting increased surface contact-is contacted with the 30 selective. absorbent in any suitable manner with or without pressure.
- resort may ,be had to the agitation of the two agents in a common vesselor to counter-current flow.
- sulfuric acid containing 45 between and msol, preferably 65% H2804 as it apparently yields the best results with 4 or 5, carbon fractions and the like. While the 3-3 fraction is in intimate contact with the sulfuric acid the temperature is kept below 50 F.
- the isobutylene dissolves in this concentration of acid while the butene-l and 'butene-Z- substantially do not, but'remain associated with" thebutane.
- the sulfuric acid solution of isobutylene is mechanically separated from the un 55 dissolved fraction in any suitable manner as known to the art. The solution of-isobutylene is then heated to an elevated temperature around 180 F.
- the polymers may be admixed with hydrocarbon fuel to' enhance the anti-knock rating of the latter.
- the recovered sulfuric acid is cooled to the desired. temperature prior to recycling in order to avoid solution of secondary-base olefines.
- the acid may be cooled prior to the separation of the polymer therefrom.
- dioleflnes When dioleflnes are present in the fraction undergoing treatment, they areselectively absorbed practically simultaneously "with the tertiarybase olefines and are removed with the solution of tertiary-base olefines.
- the selective absorbent which is recovered after separation of the polymers and recycled" to the absorption system is a dilute acid liquor which does not contain substantial amounts of alkyl sulfates.
- the continuous process for the selective re moval of tertiary-base olefines from hydrocarbon mixtures containing the same comprising contacting the hydrocarbon mixture in the liquid phase with a selective acid absorbent for the tertiary-base olefine, separating .the solution of the tertiary-base oleflne from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine, effecting the separation of the polymer from the selective absorbent and re- .cycling the recovered selective absorbent so that it is contacted with fresh hydrocarbon mixtures containing tertiary-base olefines.
- the continuous process for the selective removal of isobutylene from a hydrocarbon mixture produced by cracking petroleum oil and which consists predominantly of paraffin and olefine hydrocarbons of four carbon atoms comprising contacting the hydrocarbon mixture in the liquid phase with a selective acid absorbent for the isobutylene, separating the solution of isobutylene from the undissolved hydrocarbon mixture, polymeri'zing the dissolved isobutylene, effecting the separation of the polymer from the selective absorbent and recycling the recovered selective absorbent so that it is contacted with fresh hydrocarbon mixtures containing isobutylene.
- the continuous process for the selective removal of tertiary-base olefines fromhydrocarbon mixtures containing the same comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to,'70% H2804 content at a temperature below 90 F., separating the 9 solution of tertiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine, effecting the separation of the polymer from the acid and recycling the recovered acid'so that it is contac ted with fresh hydrocarbon mixtures containing tertiary base olefines.
- the continuousprocess for the selective prising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to H2804 content at a temperature below F., separating the solution of tertiary-base olefine from theundissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine effecting the sepcling the recovered acid so that it is contacted with fresh hydrocarbonmixtures containing tertiary-base olefines.
- tertiary-base olefines from a hydrocarbon mixture produced by cracking petroleum oil and which consists predominantly of parafin and olefine hydrocarbons of the same number of carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acidbetween 60 to 70% H2804 content at a temperature below 90 g t; separating the solution of tertiarybase olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine,'effecting the separation of the polymer from the acid and recycling the recovered acid so that it is contacted with freshhydrocarbon mixtures containing.
- i- 15 The continuous process for the selective removal of isobutylene from a hydrocarbon mixture produced by cracking petroleum oil and fine hydrocarbons of four carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to 70% H2804 content at a temperature below 90 F., separating thesolution of isobutylene from the undissolved hydrocarbon mixture, polymerizing the dissolved,
- Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and iso olefines derived from the pyrolysis of mineral oil which comprises treating said mixture in the liquid phase with aqueous sulphuric acid, under conditions of acid concentration and temperature adapted to selectively form the absorption product of the tertiary iso olefines' present in said mixture with the formation of an acid liquor containing said absorption products, removing said acid liquor, heating the same, and separating the oily polymers thereby produced.
- Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and isoolefines derived from the cracking of mineral oil, which comprises treating said mixture with aqueous sulphuric acid of from 60 to 70% acid concentration while'maintaining a temperature at which there is selectively formed the absorption products of the tertiary isoolefines present in said mixture, thereby forming an acid liquor containing said absorption products, removing said acid liquor, heating the same, and separating the oily polymers thereby produced.
- Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and isoolefines derived from the cracking of petroleum oil, which comprises treating said mixture with aqueous sulphuric acid of from 60 to 70% acid concentration at a temperature of from to 25 C. thereby selectively forming the absorption products of the tertiary isoolefines present in said mixture with the formation of an acid liquor containing said absorption products, removing said acidliquor, heating the same, and separating the oily polymers thereby produced.
- Process of producing hydrocarbons boiling within the gasoline range from a mixture of by drocarbons containing normal and isobutylene derived from the pyrolysis of mineral oil, which comprises treating said mixture in the liquid phase with aqueous sulphuric acid, under conditions of acid concentration and temperature adapted to selectively form the absorption product of the isobutylene present in said mixture with the formation of an acid liquor containing said absorption product, removing said acid liquor, heating the same, and separating the oily polymers thereby produced.
- Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and isobutylene derived from the pryrolysis of mineral oil, which comprises treating said mixture with aqueous sulphuric of from 60 to 70% acid concentration,
- Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and isobutylene derived from the pyrolysisof mineral oil, which comprises treating said mixture with aqueous sulphuric acid of from 60 to 70% acid concentration at a temperature of from 0 to 25 0., thereby selectively forming the absorption product of the isobutylene present in said mixture with the formation of an acid liquor containing said absorption product, removing said acid liquor, heating the same, and separating the oily polymers thereby produced.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
SEGRllGATION I OLE on'rEa'rIAnY BASE FINES PATENT oFF'lc William Engs and Richard Moravcc, Berkeley, Calif., assigncrs to Shell Developmentpom pany, San Francisco, Calif., a corporation of Delaware N0 Drawing. Application June 1, 1931,
g No. 541,526-
Serial 28 Claims. (01. 260-170 This invention relates to a process for the segregation of highly reactive olefines from olefinic mixtures containing more than three carbon atoms and ismore particularly concernedwith a continuous cyclic process which effects an economy in the necessary amount of selective solvent required to selectively absorb the highly reactive We have discovered that secondary alcohols can be prepared' simply and economically from olefine-containing gases of the type mentioned heretofore by practicing the selective removal of highly reactive olefines in a continuous manner wherein the selective absorbent is continuously recovered and recyc ed for further use.
The preferred mm 1 material is substantially stripped of hydrocar ons containing less than four carbonatoms and suitably fractionated into fractions containing hydrocarbons of the same number ofcarbon atoms. In certain instances,
it will be diflicult to remove traces of higher and lower carbon compounds, but their presence "is not detrimental to this 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 ofcarbon atoms. In segregating the hydrocarbons into suitable fractions, it will be found that it will be practically impossible to separate the parafiln hydrocarbons from the olefine hydrocarbons possessing the same number of carbon atoms without uneconomical and complicated procedure, As the' parafiin 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.
The fractions to be treated are thus characteristically composed of paraffin hydrocarbons, olefines, both iso-- "and normal, which yield secondary derivatives (hereinafter designated as secondary-base olefines), iso-olefines which yield phosphoric .acid are typical).
tertiary-base-olefines) and traces of diolefines such as butadiene and isoprene.
For illustrative purposes only, references will be had to a substantially pure 3-]?! fraction which represents a mixture of butane and butene obtained by distillation or condensation or both. Besides the butane there will benormally present isobutane, butene-l, butene-2 and isobutene. Isobutene is characteristic of the tentiary-base olefines as regards their high rates 10 of reactivity with various reagents. It is preferable to selectively remove the isobutene content prior to the conversion of the secondary-base olefines to secondary alcohols otherwise the ter- 7 tiary-base olefine polymerizes, causing localoverheating and thus decreasing the possible effective yields of secondary alcohols, or incom-' plete conversion of the secondary-base olefines results from the desire to avbid excessive polymerization of the tertiary-base olefine.
Selective absorbents for tertiary=base olefines are polybasic acids (of which sulfuric acid or In certain instances it may be desirable to employ monobasic acids as hydrochloric acid or organic acids as 25 benzene sulfonic acids or the sulfonic acids of the homologues of benzene.
The desired fraction," either in the gaseous or liquidstate--the liquid state promoting increased surface contact-is contacted with the 30 selective. absorbent in any suitable manner with or without pressure. For example, resort may ,be had to the agitation of the two agents in a common vesselor to counter-current flow. It is 1 desirablewhen employing a fraction in the gase- 35 ous state to conduct the process in counter-current fashion through a packed tower as this sys tem lends itself'most readily to intimate distribution of the tertiary-base olefine in the selective absorbent. Care must be taken that the 40 strengths of the selective absorbents are regu-' lated according to the temperature of the process and according to the character of the tertiary-base olefine. In practicing our invention, we preferably employ sulfuric acid containing 45 between and msol, preferably 65% H2804 as it apparently yields the best results with 4 or 5, carbon fractions and the like. While the 3-3 fraction is in intimate contact with the sulfuric acid the temperature is kept below 50 F. The isobutylene dissolves in this concentration of acid while the butene-l and 'butene-Z- substantially do not, but'remain associated with" thebutane. The sulfuric acid solution of isobutylene is mechanically separated from the un 55 dissolved fraction in any suitable manner as known to the art. The solution of-isobutylene is then heated to an elevated temperature around 180 F. which results in the formation of polymers of isobutylene which are hydrocarbonsimmiscible with sulfuric acid and therefore easily separated therefrom by any suitable operation known to the art. The polymers may be admixed with hydrocarbon fuel to' enhance the anti-knock rating of the latter. The recovered sulfuric acid is cooled to the desired. temperature prior to recycling in order to avoid solution of secondary-base olefines. The acid may be cooled prior to the separation of the polymer therefrom. Thus by continuously introducing a selective absorbent and a preferred hydrocarbon fraction ina'suitable contact vessel, selectively removing the tertiary-base olefine and continuously-recovering and recycling the selective absorbent, we have a closed, complete continuous process which furnishes a hydrocarbonfraction practically devoid of tertiary-base olefines, which yields a desirable anti-knock agent and which requires a minimum of selectiv absorbent to operate, all tending towards a flexible, easily regulatable process which constitutes an advance in the ,art relating to the preparation of secondary alcohols. I
When dioleflnes are present in the fraction undergoing treatment, they areselectively absorbed practically simultaneously "with the tertiarybase olefines and are removed with the solution of tertiary-base olefines. The selective absorbent which is recovered after separation of the polymers and recycled" to the absorption system is a dilute acid liquor which does not contain substantial amounts of alkyl sulfates.
While we have in the foregoing described in some detail the 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 'asto the reasons for the advantageous results attained. On the other hand, the invention isto be 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 ourinvention:
1. The continuous process for the selective re moval of tertiary-base olefines from hydrocarbon mixtures containing the same, comprising contacting the hydrocarbon mixture in the liquid phase with a selective acid absorbent for the tertiary-base olefine, separating .the solution of the tertiary-base oleflne from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine, effecting the separation of the polymer from the selective absorbent and re- .cycling the recovered selective absorbent so that it is contacted with fresh hydrocarbon mixtures containing tertiary-base olefines.
2. The continuous process for the selective removal of tertiary-base olefines from hydrocar- .bonmixtures containing paraffin and olefine hydrocarbons of the same number of carbon atoms,
.comprising contacting the hydrocarbon mixture in' the liquid phase with a selective acid absorbent for the tertiary-base olefine, separating the. solution of the tertiary-base oleflne from theundissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine, effecting the separation of the polymer fromthe selective absorbentand recycling the recovered selective absorbent so that it is contacted with fresh hydrocarbon mixtures containing tertiary-base olefines.
3. The continuous process for the selective removal of tertiary-base olefines from a hydrocarbon mixture produced by cracking petroleum oil and containing paraffin and olefine hydrocarbons of the same number of carbon atoms, comprising contacting the hydrocarbon mixture in the liquid phase with a selective acid absorbent for the tertiary-basevolefine, separating the solution of the tertiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine, effecting the separation of the polymer from the selective absorbent and recycling the recovered selective absorbent, so that it is contacted with fresh hydrocarbon mixtures containing tertiary-base olefines.
4. The continuous process for the selective removal of tertiary-base olefines from a hydrocarbon mixture produced by cracking petroleum oil and which consists predominantly of paraffin and olefine hydrocarbons of the same number of carbon atoms, comprising contacting the hydrocarbon mixture in the liquid phase with a selective acid absorbent for the tertiary-base olefine, separating the solution of the tertiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine, effecting the separation of the polymer from the selective absorbent and recycling the recovered selective absorbent so that it is contacted with fresh hydrocarbon mixtures containing tertiarybase olefines.
5. The continuous process for the selective removal of isobutylene from a hydrocarbon mixture produced by cracking petroleum oil and which consists predominantly of paraffin and olefine hydrocarbons of four carbon atoms, comprising contacting the hydrocarbon mixture in the liquid phase with a selective acid absorbent for the isobutylene, separating the solution of isobutylene from the undissolved hydrocarbon mixture, polymeri'zing the dissolved isobutylene, effecting the separation of the polymer from the selective absorbent and recycling the recovered selective absorbent so that it is contacted with fresh hydrocarbon mixtures containing isobutylene.
6; Thecontinuous process for the selective removal of tertiary-base olefines from hydrocarbon mixtures containing the same, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between to 70% H2304 content, separating the solution of the tertiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine, ef-
fecting the separation of the polymer from the tiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiarybase olefine, effecting the separation of the polymer from the acid and recycling the recovered acid so that it is contacted with fresh hydrocarbon mixtures containing tertiary-basepleflnes.
sulfuric acid between 60 to 70% H2804 content,
separating the solution of tertiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine; ef-
fecting the separation of the polymer from the acid and recycling the recovered acid so that it is contacted withfresh hydrocarbon mixtures containing tertiary-base -olefines. fl k 9. The continuous process for the selective removal of tertiary-base olefines from a hydrocarbon mixture produced by cracking petroleum oil and which consists predominantly of paraflin and olefine hydrocarbons of the same number of carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to 70% H2804 content, separating the solution of the tertiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolyed tertiary-base olefine, effecting the separation of the polymer from the acid and recycling the recovered acid so that it is contacted with fresh hydrocarbon mixtures containing tertiary-base removal of isobutylene from a hydrocarbon mixture produced by cracking petroleum oil and which consists predominantly of paraffin and olefine hydrocarbons of four carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to 70% H2804 content, separating the solution of-isobutylene from the undissolved hydrocarbon mixture, polymerizing the dissolved isobutylene, effecting the separation of the polymer from the acid and recycling the recovered acid so that it is contacted ,with fresh hydrocarbon mixtures containing tertiary-base olefines. I 1
11. The continuous process for the selective removal of tertiary-base olefines fromhydrocarbon mixtures containing the same, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to,'70% H2804 content at a temperature below 90 F., separating the 9 solution of tertiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine, effecting the separation of the polymer from the acid and recycling the recovered acid'so that it is contac ted with fresh hydrocarbon mixtures containing tertiary base olefines.
a 12. The continuous process for the selective removal of tertiary-base olefines from hydrocarbon mixtures containingparaflih and olefine hy- 9 drocarbons of the same number of carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between to 70% HzSO4 content at a temperature below 90 F., separating the solution of tertiary-base olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-baseolefine, effecting the separation of the polymer from the acid and recycling the recovered acid sov that itis 10. The continuousprocess for the selective prising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to H2804 content at a temperature below F., separating the solution of tertiary-base olefine from theundissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine effecting the sepcling the recovered acid so that it is contacted with fresh hydrocarbonmixtures containing tertiary-base olefines.
14. The continuous process for the selective removal of tertiary-base olefines from a hydrocarbon mixture produced by cracking petroleum oil and which consists predominantly of parafin and olefine hydrocarbons of the same number of carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acidbetween 60 to 70% H2804 content at a temperature below 90 g t; separating the solution of tertiarybase olefine from the undissolved hydrocarbon mixture, polymerizing the dissolved tertiary-base olefine,'effecting the separation of the polymer from the acid and recycling the recovered acid so that it is contacted with freshhydrocarbon mixtures containing. tertiary-base olefines:
i- 15. The continuous process for the selective removal of isobutylene from a hydrocarbon mixture produced by cracking petroleum oil and fine hydrocarbons of four carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to 70% H2804 content at a temperature below 90 F., separating thesolution of isobutylene from the undissolved hydrocarbon mixture, polymerizing the dissolved,
which consists predominantly of parafiin and oles aration of the polymer from the acid and recyundissolved hydrocarbon mixture, heating said solution to an elevated temperature sothatpolymervization of the dissolved tertiary-base olefine is effected, separating the polymer from the acid and recycling the recovered acid so that it iscon tacted with fresh hydrocarbon mixtures containing tertiary-base olefines.
17. The continuous process for the selective removal of tertiary-base, olefines from hydrocarbon mixtures containing paraffln and olefine hydrocarbons of the same number of carbonatoms,
comprising contacting the hydrocarbon mixture with aqueous sulfuric acid \between 60 to 70% 1 12804 content at atemperature below 90 It, separating the solution of the tertiary-base olefine from the undissolved hydrocarbon mixture, heating saidsolution to an elevated temperature so that polymerization of the dissolved tertiar'y base olefine i's effected, separating the polymer from the acid and recycling the recove ered acid so thatyit is contacted with fresh hydrocarbon mixtures containing tertiary-base olefines.
18. The continuous process for the selective removal of 'tertiary base olefines from'a hydrocarbon mixture produced by cracking petroleum oil and containing parafiin and olefine hydro,-
carbons of the same number of carbon atoms,
, comprising contacting the, hydrocarbon mixture with aqueous sulfuric acid between 60 to 70% H2804 content at a temperature below 90 F., separating the solution of tertiary-base olefine from the undissolved hydrocarbon mixture, heating said solution to an elevated temperature so that polymerization of the dissolved tertiarybase olefine is effected, separating the polymer from the acid and recycling the recovered acid so that it is contacted with fresh hydrocarbon mixtures containing tertiary-base olefines.
19. The continuous process for the selective removal of tertiary-base olefines from a hydrocarbon mixture produced by crackingpetroleum oil and which consists predominantly of paraflin and olefine hydrocarbons of the same number of carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60 to '70% H2804 content at a temperature below 90 F., separating the solution of tertiarybase olefines from the undissolved hydrocarbon mixture, heating said solution to an elevated temperature so that polymerization of the dissolved tertiary-base olefine is effected, separating the polymer from the acid and recycling the recovered acid so that it is contacted with fresh hydrocarbon mixtures containing tertiary-base olefines.
20. The continuous process for the selective removal of isobutylene from a hydrocarbon-mixture produced by cracking petroleum oil and which consists predominantly of paraffin and olefine hydrocarbons of four carbon atoms, comprising contacting the hydrocarbon mixture with aqueous sulfuric acid between 60lto 70% H2804 content at a temperature below 90 F., separating the solution of isobutylene from theundissolved hydrocarbon mixture, heating said solution to an elevated temperature so that polymerization of the dissolved isobutylene is effected, separating the polymer from the acid and recycling the recovered acid so that it is contacted with in the liquid phase with sulfuric acid of con-' centration below '70 per cent via absorption and subsequent heating whereby substantially only the tertiary olefine content forms polymers, separating from the acid liquor a substantial proportion of the resulting polymers and then bringing the separated acid liquor into contactwith an additional quantity of olefine mixture.
23. Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and iso olefines derived from the pyrolysis of mineral oil, which comprises treating said mixture in the liquid phase with aqueous sulphuric acid, under conditions of acid concentration and temperature adapted to selectively form the absorption product of the tertiary iso olefines' present in said mixture with the formation of an acid liquor containing said absorption products, removing said acid liquor, heating the same, and separating the oily polymers thereby produced.
24. Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and isoolefines derived from the cracking of mineral oil, which comprises treating said mixture with aqueous sulphuric acid of from 60 to 70% acid concentration while'maintaining a temperature at which there is selectively formed the absorption products of the tertiary isoolefines present in said mixture, thereby forming an acid liquor containing said absorption products, removing said acid liquor, heating the same, and separating the oily polymers thereby produced.
25. Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and isoolefines derived from the cracking of petroleum oil, which comprises treating said mixture with aqueous sulphuric acid of from 60 to 70% acid concentration at a temperature of from to 25 C. thereby selectively forming the absorption products of the tertiary isoolefines present in said mixture with the formation of an acid liquor containing said absorption products, removing said acidliquor, heating the same, and separating the oily polymers thereby produced.
26. Process of producing hydrocarbons boiling within the gasoline range from a mixture of by drocarbons containing normal and isobutylene derived from the pyrolysis of mineral oil, which comprises treating said mixture in the liquid phase with aqueous sulphuric acid, under conditions of acid concentration and temperature adapted to selectively form the absorption product of the isobutylene present in said mixture with the formation of an acid liquor containing said absorption product, removing said acid liquor, heating the same, and separating the oily polymers thereby produced.
27. Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and isobutylene derived from the pryrolysis of mineral oil, which comprises treating said mixture with aqueous sulphuric of from 60 to 70% acid concentration,
while maintaining a temperature at which there is selectively formed the absorption product of the isobutylene present in said mixture, thereby forming an acid liquor containing said absorption product, removing said acid liquor, heating the same, and separating the oily polymers thereby produced. I
28. Process of producing hydrocarbons boiling within the gasoline range from a mixture of hydrocarbons containing normal and isobutylene derived from the pyrolysisof mineral oil, which comprises treating said mixture with aqueous sulphuric acid of from 60 to 70% acid concentration at a temperature of from 0 to 25 0., thereby selectively forming the absorption product of the isobutylene present in said mixture with the formation of an acid liquor containing said absorption product, removing said acid liquor, heating the same, and separating the oily polymers thereby produced.
WILLIAM ENGS.
RICHARD MORAVEC.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US541526A US2007159A (en) | 1931-06-01 | 1931-06-01 | Segregation of tertiary base olefines |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US541526A US2007159A (en) | 1931-06-01 | 1931-06-01 | Segregation of tertiary base olefines |
Publications (1)
Publication Number | Publication Date |
---|---|
US2007159A true US2007159A (en) | 1935-07-09 |
Family
ID=24159953
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US541526A Expired - Lifetime US2007159A (en) | 1931-06-01 | 1931-06-01 | Segregation of tertiary base olefines |
Country Status (1)
Country | Link |
---|---|
US (1) | US2007159A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2420369A (en) * | 1938-06-25 | 1947-05-13 | Texas Co | Acid alkylation of isoparaffins |
US2423414A (en) * | 1943-04-07 | 1947-07-01 | United Gas Improvement Co | Process for recovering diolefins from hydrocarbon mixtures |
US2431005A (en) * | 1944-08-19 | 1947-11-18 | Standard Oil Dev Co | Recovery and regeneration of isobutenes |
US2440286A (en) * | 1944-10-16 | 1948-04-27 | Shell Dev | Interpolymerization of isoamylenes with normal butenes and isobutene |
US2567283A (en) * | 1938-06-25 | 1951-09-11 | Texas Co | Method of manufacturing motor fuels by polymerization and alkylation |
US2576535A (en) * | 1948-02-10 | 1951-11-27 | Standard Oil Co | Treating olefins with alkanesulfonic acid |
US2626959A (en) * | 1951-02-06 | 1953-01-27 | Universal Oil Prod Co | Process for extraction of olefinic hydrocarbon mixtures |
-
1931
- 1931-06-01 US US541526A patent/US2007159A/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2420369A (en) * | 1938-06-25 | 1947-05-13 | Texas Co | Acid alkylation of isoparaffins |
US2567283A (en) * | 1938-06-25 | 1951-09-11 | Texas Co | Method of manufacturing motor fuels by polymerization and alkylation |
US2423414A (en) * | 1943-04-07 | 1947-07-01 | United Gas Improvement Co | Process for recovering diolefins from hydrocarbon mixtures |
US2431005A (en) * | 1944-08-19 | 1947-11-18 | Standard Oil Dev Co | Recovery and regeneration of isobutenes |
US2440286A (en) * | 1944-10-16 | 1948-04-27 | Shell Dev | Interpolymerization of isoamylenes with normal butenes and isobutene |
US2576535A (en) * | 1948-02-10 | 1951-11-27 | Standard Oil Co | Treating olefins with alkanesulfonic acid |
US2626959A (en) * | 1951-02-06 | 1953-01-27 | Universal Oil Prod Co | Process for extraction of olefinic hydrocarbon mixtures |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2391404A (en) | Process for the separation of an unsaturated hydrocarbon from a hydrocarbon mixture | |
US2007159A (en) | Segregation of tertiary base olefines | |
US2458067A (en) | Process for separating olefins from paraffins | |
US2007160A (en) | Selective removal of tertiary base olefines | |
US2368446A (en) | Process for preparing olefins from alkyl halides | |
US2831905A (en) | Gamma-butyrolactone as a selective solvent for hydrocarbons | |
US2403972A (en) | Process for extracting an aromatic hydrocarbon from a mixture containing other hydrocarbons | |
US2958715A (en) | Tertiary amylene recovery using sulfuric acid and hydrocarbon extractants | |
US2060871A (en) | Manufacture of hydrocarbons | |
US2443245A (en) | Isobutylene purification | |
US3497569A (en) | Treatment of alkylation feed stock with sodium,potassium,or lithium hydroxide solution | |
US2560362A (en) | Acid extraction of mixed olefin hydrocarbons | |
US3082271A (en) | N-methyl pyrrolidone for the separation of olefins from hydrocarbon mixtures | |
US2348931A (en) | Process for the treatment of hydrocarbons | |
US2407386A (en) | Recovery of secondary olefins from acid extracts | |
US3864423A (en) | Alkylation of hydrocarbons | |
US2494546A (en) | Separation of olefins | |
US3437585A (en) | Olefin production and subsequent recovery | |
US3227775A (en) | Sulfuric alkylation acid recovery | |
US2078516A (en) | Process of treating acid liquors | |
US2414402A (en) | Removal of foam-producing substances from furfural employed in extractive distillation of hydrocarbons | |
US2393895A (en) | Treatment of hydrocarbons | |
US2384376A (en) | Recovery of sulphur dioxide and diolefins from sulphones | |
US2626959A (en) | Process for extraction of olefinic hydrocarbon mixtures | |
US2426082A (en) | Method for eliminating foaming in the recovery of sulfuric acid from an olefin recovery operation |