US3867475A - Isoparaffin alkylation - Google Patents
Isoparaffin alkylation Download PDFInfo
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- US3867475A US3867475A US343322A US34332273A US3867475A US 3867475 A US3867475 A US 3867475A US 343322 A US343322 A US 343322A US 34332273 A US34332273 A US 34332273A US 3867475 A US3867475 A US 3867475A
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- carbon dioxide
- acid
- alkylation
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- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 53
- 230000029936 alkylation Effects 0.000 title description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 50
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 49
- 239000003377 acid catalyst Substances 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- -1 olefin hydrocarbon Chemical class 0.000 claims abstract description 10
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 9
- 239000002168 alkylating agent Substances 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000001282 iso-butane Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 6
- 230000006872 improvement Effects 0.000 claims description 5
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 230000002152 alkylating effect Effects 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 13
- 150000008051 alkyl sulfates Chemical class 0.000 abstract description 3
- 229960004424 carbon dioxide Drugs 0.000 description 43
- 239000003054 catalyst Substances 0.000 description 18
- 150000001336 alkenes Chemical class 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 8
- FLTJDUOFAQWHDF-UHFFFAOYSA-N 2,2-dimethylhexane Chemical class CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HWBLTYHIEYOAOL-UHFFFAOYSA-N Diisopropyl sulfate Chemical compound CC(C)OS(=O)(=O)OC(C)C HWBLTYHIEYOAOL-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- UXLGPJLQZVPSSD-UHFFFAOYSA-N bis(2-methylpropyl) sulfate Chemical compound CC(C)COS(=O)(=O)OCC(C)C UXLGPJLQZVPSSD-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- LMEDOLJKVASKTP-UHFFFAOYSA-N dibutyl sulfate Chemical compound CCCCOS(=O)(=O)OCCCC LMEDOLJKVASKTP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002968 pentalenes Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/03—Acids of sulfur other than sulfhydric acid or sulfuric acid, e.g. halosulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
- C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
Definitions
- Benefits of the present invention are obtained by dissolving carbon dioxide into the liquid strong acid catalyst. Maximum benefits are obtained when the strong acid is saturated with carbon dioxide at the alkylation reaction conditions employed. In order to encourage solution of carbon dioxide in strong acid, it is usually desirable to employ an excess of carbon dioxide. In treating the strong acid, weight ratios of carbon dioxide to strong acid of about 0.1/100 and higher may be employed. Preferably weight ratios of carbon dioxide to strong acid of at least 5/100 are employed. Great excesses of carbon dioxide to strong acid in the acid treatment are not necessary,
- Contact time of carbon dioxide with strong acid being treated need only be sufficient for solution of the desired amount of carbon dioxideint'o the strong acid. Contact times of from a few seconds to 24 hours and longer may be employed. Necessary contact time will be shorter with better mixing and more intimate contact of carbon dioxide with the strong acid. Preferred contact times for any particular acid treating system may be easily established by observing the rate of solution of carbon dioxide into the strong acid under the conditions of pressure, temperature and degree of mixing present in the particular system under consideration.
- alkylation reactions contemplated in the present invention are carried out in the liquid phase.
- the reactants need not be normally liquid hydrocarbons.
- Alkylation reaction conditions can vary in temperature from below zero to about 100F., and can be carried out at pressures of from atmospheric to 1000 psig and higher.
- olefin space velocities of from about 0.01 to about volumes olefin/hour/volume of catalyst may be employed.
- Molar ratios of isoparaffin hydrocarbonto alkylati'ng agent of from about 1:1 to about 50:1 and higher may be emloyed.
- substantial molar excess of isoparaffin to olefin is maintained in an alkylation reaction, with molar ratios of isoparaffin to olefin of'from about 5:1 to about 20:1 being particularly preferred.
Abstract
A strong acid catalyzed alkylation process wherein an isoparaffin is alkylated with an alkylating agent such as olefin hydrocarbon, alkyl sulfates, in the liquid phase, at a superatmospheric pressure and a temperature in the range of from below zero to about 100*F., and wherein gaseous carbon dioxide is dissolved in the strong acid catalyst.
Description
Unlted States Patent 1191 1111 3,867,475
Estes et al. Feb. 18-, 1975 [5 ISOPARAFFIN ALKYLATION 2,468,529 4/1949 Voorhies et a]. 260/683.59
2,520,391 8/1950 Findlay 260/683.59 [75] John Estes P B Falls 3,489,818 1/1970 Hcrvert 260/68351 g y Cole, Flshklll, both of 3,531,546 9/1970 Hervert.....p.' 260/683.51
[73] Assignee: Texaco Inc., New York, NY. Primary Examiner-Paul M- Coughlan,
Attorney, Agent, or Firm-Th0mas H. Whaley; C. G. [22] Flledz Mar. 21, 1973 Ries [21] Appl. No.: 343,322
[57] ABSTRACT 52 us. c1 260/683.63, 252/436, 260/683.58 A Strong acid catalyzed alkylation process wherein an 51 1111.01. C076 3/54 isoparaffin is alkylated with an alkylating agent Such [58] Field of Search..... 260/683.63, 683.51, 683.59; 88 Olefin hydrocarbon, alkyl sulfates, in the qu 252/436 phase, at a superatmospheric pressure and a temperature in the range of from below zero to about 100F., 5 References Qit d and wherein gaseous carbon dioxide is dissolved in the UNITED STATES PATENTS 2,286,184 6/1942 Bradley et al 260/683.63 5 Claims, N0 Drawings ISOPARAFFIN ALKYLATION BACKGROUND OF THE INVENTION The present invention relates to alkylation of isoparaffin hydrocarbons with olefins in the presence of a strong acid catalyst. Particularly, the invention relates to production of C C hydrocarbon suitable for use as motor fuel by alkylation of isoparaffin hydrocarbon with olefins. More particularly, this invention relates to an isobutane-butylene alkylation process catalyzed by sulfuric acid and/or flurosulfonic acid, having high selectivity for production of trimethyl pentanes.
Acid catalyzed alkylation wherein an-alkane is added to an alkene is well known. The alkylation reaction is generally carried out in the liquid phase at a temperature usually below about 100F.'and at a pressure sufficient to maintain reactants in the liquid phase. Of particular importance is alkylation of isobutane with butylene to form octane hydrocarbons, especially trimethyl pentanes, which are useful as components of motor fuel. The butylenes which may be a mixture of normal and isobutylenes are reacted with a molar excess of isobutane in the liquid phase in the presence of a strong acid such as sulfuric acid, flurosulfonic acid, and mixtures thereof, at a temperature of F. to 100F. and a pressure of 10 to 150 psig, or higher.
The discussion herein is presented with respect to formation of octane hydrocarbons, however, it is to be understood that the discussion is equally applicable to alkylation reactions generally, and particularly to alkylation of isobutane and isopentane with lower molecular weight olefms such as propylene. butylenes, and pentalenes. Basically, it is desirable in an alkylation reaction to promote formation of the 1:1 olefin-paraffin adduct. That is, formation of octane from butylenes and paraffins. In strong acid catalyzed alkylation reactions, side reactions occur in which C products are formed as well as the desirable 1:1 olefin-paraffin adduct. A portion of C products then undergo cracking to form undesirable lighter hydrocarbons, such as for example, C C and C light alkylate hydrocarbons. The result of such side reactions,then, is to reduce production of the desired C products and to lower the octane number of the alkylate product obtained.
SUMMARY OF THE INVENTION Now, according to the method of the present invention, an improved strong acid catalyzed alkylation processis disclosed wherein production of desirable 1:1 olefin-isoparaffin adduct is increased. In the method of the present invention, olefin hydrocarbon is reacted with a molar excess of isoparaffm hydrocarbon at a temperature of from about 0F. to about 100F., a pressure of about 10 psig to about 150 psig and higher, in the presence of a carbon dioxide treated strong acid catalyst such as sulfuric acid, flurosulfonic acid and mixtures thereof. In a preferred embodiment, the carbon dioxide treated strong acid catalyst is prepared by contacting liquid strong acid with carbon dioxide gas at a temperature in the range of 0F. to 75F.,' a pressure in the range of 50 psig to 1000 psig and under condilyst of the prior art is employed. Additionally, formation of undesirable, low octane number light alkylate and heavy alkylate hydrocarbons is decreased. In an alkylation process of the present invention, employing a carbon dioxide treated strong acid catalyst, wherein isobutane is alkylated with butylenes, octane hydrocarbons are the major product of the process. Also, the major portion of the octane hydrocarbon alkylate is comprised of trimethyl pentanes which have high octane numbers and are particularly desirable as components for gasoline blending. Reduction of light alkylate components and C; heavy alkylate components, by following the method of the present invention, improves volatility characteristics of the alkylate product.
These, and other advantages will be more fully set out 7 in the detailed description of the invention which follows.
DETAILED DESCRIPTION OF THE INVENTION Unexpectedly,according to the present invention, we have discovered that incorporation of carbon dioxide gas into liquid alkylation acid catalysts improves subsequent alkylation reactions by increasing the yield of desirable 1:1 isoparaffin-olefin adducts, particularly the desirable highly branched isomers. The reasons for such improvement are not presently known. It may be speculated that solution of carbon dioxide into the acid catalyst reduces the acid viscosity such that better mixing of hydrocarbon reactant and catalyst is obtained, or that hydrocarbon solubility in the acid catalyst is'increased. However, such speculations are unsupported and are not to be taken as limitations upon the present invention.
Carbon dioxide treatment according to the method of the present invention is applicable to strong Bronsted acid alkylation catalysts. The strong Bronsted acids are those which readily give up a proton, and include HF as well as H H SO SO H SO H- acids are the catalysts used in the (C to C isoparafinto the liquid catalyst. Preferably, liquid acid and gase-- ous carbon dioxide are contacted under conditions of intimate mixing at superatmospheric pressures and temperatures in the range of below zero to 100F. More perferably, pressures in the range of about 50 1000 psig tions of good mixing to dissolve carbon dioxide into the andtemperatures in the range of 2075F. are em .ployed. Higher pressures and lower temperatures favor solution of carbon dioxide in the liquid strong acid. Pressures of atmospheric and higher are effective, and pressures of at least 50 psig are preferred. Pressures greater than about 1000 psigdo not offer any substan-. tial economic advantage. Lower temperatures favor solution of carbon dioxide in liquid strong acid. At temperatures below about 20F., liquid viscosity increases substantially and extra refrigeration must be provided.
Temperatures in the range of about 20-60F. are
within the usual temperature range of the alkylation reactions contemplated herein, thus extra refrigeration to cool the liquid strong acid is not required. Benefits of the present invention are obtained by dissolving carbon dioxide into the liquid strong acid catalyst. Maximum benefits are obtained when the strong acid is saturated with carbon dioxide at the alkylation reaction conditions employed. In order to encourage solution of carbon dioxide in strong acid, it is usually desirable to employ an excess of carbon dioxide. In treating the strong acid, weight ratios of carbon dioxide to strong acid of about 0.1/100 and higher may be employed. Preferably weight ratios of carbon dioxide to strong acid of at least 5/100 are employed. Great excesses of carbon dioxide to strong acid in the acid treatment are not necessary,
and excess carbon dioxide which does not dissolve in treated strong acid may be recovered for treatment of additional acid.
Intimate mixing of carbon dioxide gas with liquid strong acid may be accomplished by any effective gasliquid contact means such as asperation, sparging, agitation, etc. In a preferred mode of operation, carbon dioxide and strong acid are contacted before employing the treated strong acid as catalyst in an alkylation reaction. In processes wherein alkylation acid is recycled from an acid settler to an alkylation reaction zone, the recycle acid may be conveniently treated with carbon dioxide in a separate treatingzone prior to introduction into the alkylation reaction zone. However, if desired, the carbondioxide may be introduced directly into the alkylation reaction zone with mixing means provided to ensure contact of acid catalyst with hydrocarbon reactants also being used to contact the acid catalyst with the carbon dioxide.
Contact time of carbon dioxide with strong acid being treated need only be sufficient for solution of the desired amount of carbon dioxideint'o the strong acid. Contact times of from a few seconds to 24 hours and longer may be employed. Necessary contact time will be shorter with better mixing and more intimate contact of carbon dioxide with the strong acid. Preferred contact times for any particular acid treating system may be easily established by observing the rate of solution of carbon dioxide into the strong acid under the conditions of pressure, temperature and degree of mixing present in the particular system under consideration.
Conventional strong acid catalyzed alkylation reactions may be carried out employing the improved process of the present invention. Thus, the alkylation can comprise reaction of an isoparaffln with an olefin or other alkylating agent. In sulfuric acid and flurosulfonic acid catlyzed alkylation reactions, alkylsulfates, such as diisopropylsulfate, diisobutylsulfate, dibutylsulfate, etc., may replace the corresponding olefin in whole or in part as alkylating agent.
The alkylation reactions contemplated in the present invention are carried out in the liquid phase. However, the reactants need not be normally liquid hydrocarbons. Alkylation reaction conditions can vary in temperature from below zero to about 100F., and can be carried out at pressures of from atmospheric to 1000 psig and higher. For continuous'processes, olefin space velocities of from about 0.01 to about volumes olefin/hour/volume of catalyst may be employed. Molar ratios of isoparaffin hydrocarbonto alkylati'ng agent of from about 1:1 to about 50:1 and higher may be emloyed. Preferably, substantial molar excess of isoparaffin to olefin is maintained in an alkylation reaction, with molar ratios of isoparaffin to olefin of'from about 5:1 to about 20:1 being particularly preferred.
Strong acid alkylation catalysts can be employed in the alkylation reactions. However, sulfuric acid and mixtures of sulfuric acid and flurosulfonic acid are preferred. 1n the process of the present invention,.where a carbon dioxide treated strong acid catalyst is employed, the preferred temperatures for use of sulfuric acid are between 30 and F. and preferred'pressures are 50 psig to 150 psig and higher. When using flurosulfonic acid as catalyst, preferred temperatures are betwen 0and 75F. and preferred pressures are 50 psig to 150 psig and higher.
The following examples are offered to illustrate the improvement of the present invention.
EXAMPLE I To demonstrate the present invention, 300 ml. of 94.43 weight percent sulfuric acid, containing'30 ml'. of acid from a previous alkylation run, was charged to a reactor equipped with cooling coils and a stirrer. The autoclave was pressured to psig with CO and the acid was stirred at about 50F. for 15 minutes. Upon .completion of the stirring, the autoclave was depressured to 50 psig and 77 grams of hydrocarbon comprising isobutane and butene-2 in a volume ratio of 6.25/1 was charged to the reactor. Under alkylation conditions including a temperature of 50F., a pressure of about psig and constant stirring, the acidhydrocarbon mixture was allowed to react for 15 min utes. At the end of the reaction time the stirring was stopped and the reaction mixture was separated into an TABLE] Treating Gas I CO Alkylate yield, basis olefin consumed (wt.71)
Alkylate Composition (Vol.7!)
C, 2.3 3.6 C 4.8 5.6 C, 4.7 5.7 Cu 56.4 53.6 C 31.9 '.31.4 Alkylate Bromine No. 2.6 3.8 C, Distribution (Vol. 7!
- of Alkylate) Trimethyl pentane 43.1 36.9 Dimethyl hexane 3.0 3.6 Unidentified C 10.3 3.1
From the Table l itcan readily be seen that the alkylation reaction employing carbon dioxide treated sulfuric acid catalyst was more selective for production of desirable C range alkylate, and particularly for production of desirable trimethyl pentanes than was the alkylation reaction employing nitrogen treated sulfuric acid catalyst. Additionally, the bromine number, indicating degree of unsaturat ion, was lower for alkylate produced in the reaction using the carbon dioxide treated sulfuric acid catalyst.
EXAMPLE II In the same reactor system employed in Example I, additional alkylation reactions were performed to show the advantage of using the carbon dioxide treated sulfuric acid of the present invention, as compared to alkylation reactions using untreated sulfuric acid. Summaries of operating conditions and analytical results for these alkylation runs are shown in Table lI below.
TABLE 11 Run Number 1 2 3 4 5 6 7 Acid (M1) 100 100 100 100 100 100 100 H SO,(wt. '7: in acid) 94.6 96.13 96.13 96.1 94.6 96.13 94.6 CO treating pressure (psig) 600 75 80 85 CO wt. of Acid 0.3 0.6 0.8 0 0 0 Hydrocarbon Charge (gms) 78 72 78 75 78 76 76 lsobutane/butene-Z ratio 6.4/1 6.6/1 6.6/1 6.6/1 6.4/1 6.6/1 6.6/1 Alkylation temperature (F.) 47-50 50 50 50 50 50 Alkylation pressure (psig) 95 80 45 60 55 Alkylation reaction time (min) 15 15 l5 15 15 15 15 Alkylate recoveryv pent-ane and heavier (gms) 20.4 17.5 19.6 21.3 14.9 15.5 19.4 Alkylate yield (wt.7z olefin) 192 195 190 205 142 149 170 Alkylate composition (VF/1.7!)
C 2.1 2.5 2.5 2.0 1.4 2.7 3.0 C 4.3 5.0 5.0 4.8 3.3 5.6 5.6 C 4.3 4.9 4.8 4.9 4.0 5.8 5.5 Cg 72.3 61.9 62.6 60.4 60.6 63.1 59.0 C 17.0 25.6 25.1 27.9 30.7 22.6 26.7 Alkylate Bromine Number 1.7 3.0 3.4 4.2 5.4 3.0 4.6 C fraction composition (Vol.7;
of Alkylate) Trimethyl pentane 58.0 49.2 50.9 47.0 42.8 46.2 43.3 Dimethyl hexane 4.7 3.2 3.8 4.4 4.9 4.6 Unidentified C, 9.6 10.5 11.7 9.8 13.3 12.0 11.1
Runs 1 through 4 were made employing carbon dioxide treated sulfuric acid alkylation catalyst. ln run 1, sulfuric acid was mixed with carbon dioxide at 600 psig and 50F. for 48 hours. At the end ofthis time, pressure was reduced and the alkylation reaction was performed at psig. ln Runs 24, carbon dioxide was added to the sulfuric acid in the reaction vessel, in the weight fractions shown and the alkylation reactions were performed at the resulting pressures. For runs 57, no additive was employed with the sulfuric acid catalyst.
From an examination of the results obtained in this example, alkylation runs employing carbon dioxide treated sulfuric acid catalyst produce greater yields of alkylate, as a weight percent of olefin consumed in the reaction, than alkylation runs employing untreated acid catalyst. Also, the alkylate from the treated catalyst runs contains greater amounts of Chg hydrocarbons, particularly the desirable trimethyl pentane isomers. As indicated by the Bromine number, olefin content of alkylate produced with treated catalyst is lower than for alkylate produced with untreated catalyst.
From the foregoing discussion and examples, the advantages of the improvement of the present invention can readily be seen. By employing a carbon dioxide treated sulfuric acid alkylation catalyst in the alkylation of lower molecular weight isoparaffin hydrocarbons with olefins having three to five carbon atoms, alkylate of improved quality can readily be obtained.
Obviously, many modifications and variations of the an acid catalyst selected from the group consisting of sulfuric acid. fluorosulfonic acid, and mixtures thereof at a temperature in the range of about zero to about F and a superatmospheric pressure; the improvement'which comprises:
a. treating said acid catalyst with carbon dioxide to form an acid catalyst having a weight ratio of carbon dioxide to acid of at least 0. 1/100 at a temperature in the range of about zero to about 100F and a superatmospheric pressure in the range of from about 50 psig to about 1000 psig; and
b. alkylating said isoparaffin hydrocarbon with said alkylating agent in the presence the carbon dioxide treated acid catalyst of step (a).
2. The process of claim 1 wherein the treating step (a) temperature is in the range of about 20F to about 75F, the pressure is in the range of about 50 psig to about 1000 psig, and the acid catalyst is contacted with carbon dioxide in a weight ratio of carbon dioxide to acid in the range of about 0.3/100 to about 5/100.
3. The process of claim 2 wherein treated acid catalyst from step (a) contains from about 0.3 to about 0.8 weight percent carbon dioxide;
4. The process of claim 3 wherein isoparaffin reactant is isobutane and the alkylating agent is selected from the group consisting of propylene, butylenes, pentylenes and mixtures thereof.
5. The process of claim 4 wherein the acid catalyst is sulfuric acid.
Claims (5)
1. IN AN ALKYLATION PROCESS WHEREIN ISOPARAFFIN HYDROCARBON SELECTED FROM THE GROUP CONSISTING OF ISOBUTANE, ISOPENTANE AND MIXTURES THEREOF IS ALKYLATED WITH AN ALKYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF PROPYLENE, BUTYLENES, PENTYLENES, THEIR SULFATES, AND MIXTURES THEREOF IN THE LIQUID PHASE, IN THE PRESENCE OF AN ACID CATALYST SELECTED FROM THE GROUP CONSISTING OF SULFURIC ACID, FLUOROSULFONIC ACID, AND MIXTURES THEREOF AT A TEMPERATURE IN THE RANGE OF ABOUT ZERO TO ABOUT 100*F AND A SUPERATMOSPHERIC PRESSURE, THE IMPROVEMENT WHICH COMPRISES: A. TREATING SAID ACID CATALYST WITH CARBON DIOXIDE TO FORM AN ACID CATALYST HAVING A WEIGHT RATIO OF CARBON DIOXIDE TO ACID OF AT LEAST 0.1/100 AT A TEMPERATURE IN THE RANGE OF ABOUT ZERO TO ABOUT 100*F AND A SUPERATMOSPHERIC PRESSURE IN THE RANGE OF FROM ABOUT 50 PSIG TO ABOUT 1000 PSIG, AND B. ALKYLATING SAID ISOPARAFFIN HYDROCARBON WITH SAID ALKYLATING AGENT IN THE PRESENCE THE CARBON DIOXIDE TREATED ACID CATALYST OF STEP (A).
2. The process of claim 1 wherein the treating step (a) temperature is in the range of about 20*F to about 75*F, the pressure is in the range of about 50 psig to about 1000 psig, and the acid catalyst is contacted with carbon dioxide in a weight ratio of carbon dioxide to acid in the range of about 0.3/100 to about 5/100.
3. The process of claim 2 wherein treated acid catalyst from step (a) contains from about 0.3 to about 0.8 weight percent carbon dioxide.
4. The process of claim 3 wherein isoparaffin reactant is isobutane and the alkylating agent is selected from the group consisting of propylene, butylenes, pentylenes and mixtures thereof.
5. The process of claim 4 wherein the acid catalyst is sulfuric acid.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US343322A US3867475A (en) | 1973-03-21 | 1973-03-21 | Isoparaffin alkylation |
JP49009021A JPS5227121B2 (en) | 1973-03-21 | 1974-01-22 | |
GB556074A GB1447565A (en) | 1973-03-21 | 1974-02-06 | Isoparaffin alkylation |
FR7406270A FR2222335B1 (en) | 1973-03-21 | 1974-02-25 | |
BE141530A BE811734A (en) | 1973-03-21 | 1974-02-28 | ALKYLATION PROCESS |
DE2411102A DE2411102A1 (en) | 1973-03-21 | 1974-03-08 | PROCESS FOR ALKYLATING ISOPARAFFINS WITH ALKYLATING AGENTS IN THE PRESENCE OF A STRONG ACID CATALYST |
CA194,762A CA1030560A (en) | 1973-03-21 | 1974-03-12 | Isoparaffin alkylation |
NL7403476A NL7403476A (en) | 1973-03-21 | 1974-03-15 | |
IT12658/74A IT1051202B (en) | 1973-03-21 | 1974-03-25 | ISOPARAPHINE ALCHILATION PROCEDURE WITH OLEFINS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US343322A US3867475A (en) | 1973-03-21 | 1973-03-21 | Isoparaffin alkylation |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/484,095 Division US3972786A (en) | 1974-06-28 | 1974-06-28 | Mechanically enhanced magnetic memory |
Publications (1)
Publication Number | Publication Date |
---|---|
US3867475A true US3867475A (en) | 1975-02-18 |
Family
ID=23345629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US343322A Expired - Lifetime US3867475A (en) | 1973-03-21 | 1973-03-21 | Isoparaffin alkylation |
Country Status (9)
Country | Link |
---|---|
US (1) | US3867475A (en) |
JP (1) | JPS5227121B2 (en) |
BE (1) | BE811734A (en) |
CA (1) | CA1030560A (en) |
DE (1) | DE2411102A1 (en) |
FR (1) | FR2222335B1 (en) |
GB (1) | GB1447565A (en) |
IT (1) | IT1051202B (en) |
NL (1) | NL7403476A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984352A (en) * | 1974-05-06 | 1976-10-05 | Mobil Oil Corporation | Catalyst containing a Lewis acid intercalated in graphite |
US4008178A (en) * | 1974-11-04 | 1977-02-15 | Texaco Inc. | Alkylation catalyst for production of motor fuels |
US4038212A (en) * | 1975-03-24 | 1977-07-26 | Texaco Inc. | Alkylation process for production of motor fuels |
US5179052A (en) * | 1991-03-04 | 1993-01-12 | Texaco Chemical Company | One step synthesis of metyl t-butyl ether from 5-butanol using fluorosulfonic acid-modified zeolite catalysts |
KR100332222B1 (en) * | 1999-06-17 | 2002-04-12 | 유승렬 | Method for Preparing Heavy Alkylate and Use Thereof |
WO2010033273A1 (en) * | 2008-09-19 | 2010-03-25 | Catalytic Distillation Technologies | Process for the alkylation of isobutane with dilute propylene |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2286184A (en) * | 1938-05-14 | 1942-06-16 | Union Oil Co | Process for producing paraffinic hydrocarbons |
US2468529A (en) * | 1945-12-13 | 1949-04-26 | Standard Oil Dev Co | Alkylation process |
US2520391A (en) * | 1947-01-20 | 1950-08-29 | Phillips Petroleum Co | Liquid-liquid contacting |
US3489818A (en) * | 1968-12-27 | 1970-01-13 | Universal Oil Prod Co | Temperature control of alkylation reactions |
US3531546A (en) * | 1967-11-29 | 1970-09-29 | Universal Oil Prod Co | Alkylation of organic compounds |
-
1973
- 1973-03-21 US US343322A patent/US3867475A/en not_active Expired - Lifetime
-
1974
- 1974-01-22 JP JP49009021A patent/JPS5227121B2/ja not_active Expired
- 1974-02-06 GB GB556074A patent/GB1447565A/en not_active Expired
- 1974-02-25 FR FR7406270A patent/FR2222335B1/fr not_active Expired
- 1974-02-28 BE BE141530A patent/BE811734A/en unknown
- 1974-03-08 DE DE2411102A patent/DE2411102A1/en active Pending
- 1974-03-12 CA CA194,762A patent/CA1030560A/en not_active Expired
- 1974-03-15 NL NL7403476A patent/NL7403476A/xx not_active Application Discontinuation
- 1974-03-25 IT IT12658/74A patent/IT1051202B/en active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2286184A (en) * | 1938-05-14 | 1942-06-16 | Union Oil Co | Process for producing paraffinic hydrocarbons |
US2468529A (en) * | 1945-12-13 | 1949-04-26 | Standard Oil Dev Co | Alkylation process |
US2520391A (en) * | 1947-01-20 | 1950-08-29 | Phillips Petroleum Co | Liquid-liquid contacting |
US3531546A (en) * | 1967-11-29 | 1970-09-29 | Universal Oil Prod Co | Alkylation of organic compounds |
US3489818A (en) * | 1968-12-27 | 1970-01-13 | Universal Oil Prod Co | Temperature control of alkylation reactions |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984352A (en) * | 1974-05-06 | 1976-10-05 | Mobil Oil Corporation | Catalyst containing a Lewis acid intercalated in graphite |
US4008178A (en) * | 1974-11-04 | 1977-02-15 | Texaco Inc. | Alkylation catalyst for production of motor fuels |
US4038212A (en) * | 1975-03-24 | 1977-07-26 | Texaco Inc. | Alkylation process for production of motor fuels |
US5179052A (en) * | 1991-03-04 | 1993-01-12 | Texaco Chemical Company | One step synthesis of metyl t-butyl ether from 5-butanol using fluorosulfonic acid-modified zeolite catalysts |
KR100332222B1 (en) * | 1999-06-17 | 2002-04-12 | 유승렬 | Method for Preparing Heavy Alkylate and Use Thereof |
WO2010033273A1 (en) * | 2008-09-19 | 2010-03-25 | Catalytic Distillation Technologies | Process for the alkylation of isobutane with dilute propylene |
US20100076241A1 (en) * | 2008-09-19 | 2010-03-25 | Loescher Mitchell E | Process for the alkylation of isobutane with dilute propylene |
US8034988B2 (en) | 2008-09-19 | 2011-10-11 | Catalytic Distillation Technologies | Process for the alkylation of isobutane with dilute propylene |
EA017873B1 (en) * | 2008-09-19 | 2013-03-29 | Каталитик Дистиллейшн Текнолоджиз | Process for the alkylation of isobutane with dilute propylene |
Also Published As
Publication number | Publication date |
---|---|
NL7403476A (en) | 1974-09-24 |
FR2222335B1 (en) | 1978-01-06 |
JPS5227121B2 (en) | 1977-07-19 |
BE811734A (en) | 1974-08-28 |
FR2222335A1 (en) | 1974-10-18 |
CA1030560A (en) | 1978-05-02 |
DE2411102A1 (en) | 1974-09-26 |
IT1051202B (en) | 1981-04-21 |
GB1447565A (en) | 1976-08-25 |
JPS49125301A (en) | 1974-11-30 |
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