US3912463A - Hydrocarbon conversion process - Google Patents

Hydrocarbon conversion process Download PDF

Info

Publication number
US3912463A
US3912463A US518140A US51814074A US3912463A US 3912463 A US3912463 A US 3912463A US 518140 A US518140 A US 518140A US 51814074 A US51814074 A US 51814074A US 3912463 A US3912463 A US 3912463A
Authority
US
United States
Prior art keywords
olefins
zone
alcohol
unreacted
isobutane
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
Application number
US518140A
Inventor
Robert H Kozlowski
Robert P Sieg
John W Scott
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron Research and Technology Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US00050123A external-priority patent/US3849082A/en
Application filed by Chevron Research and Technology Co filed Critical Chevron Research and Technology Co
Priority to US518140A priority Critical patent/US3912463A/en
Application granted granted Critical
Publication of US3912463A publication Critical patent/US3912463A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/185Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852Ethers; Acetals; Ketals; Orthoesters

Abstract

A process for producing gasoline blending stock which comprises (a) feeding an alcohol and a light hydrocarbon mixture containing at least tertiary olefins, linear olefins and isobutane to an etheration zone, (b) reacting the alcohol with the tertiary olefins in the etheration zone to obtain an ether and unreacted linear olefins and isobutane, (c) separating the ether from the linear olefins and isobutane, (d) feeding water and at least the linear olefins to a hydration zone, (e) reacting water with at least a portion of the linear olefins in the hydration zone to obtain at least a secondary alcohol, (f) separating unreacted olefins and paraffins from the secondary alcohol, (g) feeding at least a portion of the unreacted olefins and paraffins to an alkylation plant for reaction to obtain an alkylate, and (h) blending at least portions of the ether, product alcohol and alkylate to produce a gasoline blending stock.

Description

' United States Patent [191 Kozlowski et al.
[4 1 Oct. .14, 1975 HYDROCARBON CONVERSION PROCESS Primary ExaminerDaniel E. Wyman [75] Inventors: Robert H. Kozlowski, Berkeley; A t t E Y H Sm th Robert P. Sieg Piedmont; John w. 1 'Scott, Ross, all Of Calif. 3:3 :53 38 3; f 1 g Magdeburger; R H- [73] Assignee: Chevron Research Company, San
Francisco, Calif. [57] ABSTRACT [22] F1led: Oct. 25, 1974 A process for producing gasoline blending stock which [211 App! 518,140 comprises (a) feeding an alcohol and a light hydrocar- Related Application m bon mixture containing at least tertiary olefins, linear [63] Continuation-impart of Ser. No. 50,123, June 26, Plefins and lsobutne to an e theratlon (b) react- ]970 Pat No' 3,849,082 ing the alcohol w th the ternary olefins 1n the etheratlon zone to obtain an ether and unreacted linear ole- 52 us. c1. 44/56; 260/614 A; 260/641 fi and isobutane; F Separating ether from the 51 int. (:1. 0101. 1/18 lmear olefins and lsobutane (d) fedmg Water and at [58] Field of Search 44/56, 77; 260/614 A, 641 E the olefins to a P Zfme, (6)
mg water w1th at least a portion of the l1near olefins 1n [56] References Cited the hydration Zone to obtain at least a secondary alco- UNITED STATES PATENTS hol, (f) separatlng unreacted olefins and paraffins I from the secondary alcohol, (g) feeding at least a por- 2,118,881 5/ 1922; Francis 26O/6414X tion of the unreacted olefins and paraff-ms to an alky 60 2 et a lation plant for reaction to obtain an alkylate, and (h) 3O07782 1 H1961 blending at least portions of the ether, product alcohol rown et a1. 44/56 3,224,848 12/1965 Henderson... 44/56 and alkylate to Produce a gasolme blendmg Stock- 3,482,952 12/1969 Sieg et al. 44/56 3,530,060 9/1970 Offenhauer 208/60 8 Clams 1 Drawmg F'gure u N R 1-: ACT E D WATER V RC4 OLEl-"INS IZATION m m 15/ BUTA N E s n 1 17 ALCOHOL 2 g ,8
a 3 2 s HYDROCARBON UNREACTED UNREACTED Z WETHERATION OLEFINS VHYDRATION PARAFFINS lc ALKYLATION PARAFFINS OLEFINS I 9 j g 5 o 8 4 I 8 ,9 I M; 5+ Z ETHERS ALKYLATE I-IYDROCARBON CONVERSION PROCESS CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of copending application Ser. No. 50,123, filed June 26, 1970, now U.S. Pat. No. 3,849,082, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION The present invention relates to a combination process to produce a gasoline blending stock. More particularly, the present invention relates to a process combination involving etheration, hydration, and alkylation to produce a gasoline blending stock.
Previously, high-octane gasoline has generally been produced by blending lead compounds as, for example, tetramethyl lead or tetraethyl lead, with gasoline. However, it is presently believed that lead compounds in gasoline contribute to air pollution or that lead compounds in the gasoline increase the difficulty of controlling emissions from internal combustion engines.
Components such as ethers have been suggested as blending components for gasoline, but few over-all processes have been suggested for producing etherated gasolines. US. Pat. No. 3,482,952 suggests a process for producing etherated gasoline.
According to the process disclosed in US. Pat. No. 3,482,952, etherated gasoline is produced by reacting C -C tertiary olefins obtained from a cracking reactor with a lower alcohol to obtain ethers. These ethers are then blended with at least one other hydrocarbon stream.
SUMMARY OF THE INVENTION According to the present invention, a process is provided for producing a gasoline blending stock which process comprises (a) feeding an alcohol and a light hydrocarbon mixture containing at least tertiary olefins, linear olefins and isobutane to an etheration zone, (b) reacting the alcohol with the tertiary olefins in the etheration zone to obtain an ether and unreacted linear olefins and isobutane, (c) separating the ether from the linear'olefins and isobutane, (d) feeding water and at least a portion of the linear olefins to a hydration zone, (e) reacting the water with at least a portion of the linear olefins in the hydration zone to obtain a secondary alcohol, (f) separating unreacted olefins and paraffins from the secondary alcohol, (g) feeding at least a portion of the unreacted olefins and paraffins to an alkylation plant for reaction to obtain an alkylate, and (h) blending at least portions of the ether, product alcohol and alkylate to produce a gasoline blending stock.
According to a preferred embodiment of the present invention, both the isobutane and linear olefins are fed to the hydration zone and unreacted isobutane and unreacted linear olefins are withdrawn from the hydration zone and are fed to an alkylation plant to form an alkylate.
In the present specification, the term tertiary olefin is used to mean those olefins containing a carbon atom bonded to three other carbon atoms with one of the bonds being a double bond. The term linear olefin" is used in the present specification to mean olefins other than tertiary olefins and thus to include branched-chain olefins wherein the branching does not result in a tertiary olefin. Thus, the term linear olefin includes propylene, butene-Z, etc.
, According to a particularly preferred embodiment of the present invention, the light hydrocarbon mixture which is fed to the etheration zone contains normal butane in addition to tertiary olefins, linear olefins and isobutane, and, after passing through the etheration and hydration zones, the normal butane is isomerized to obtain isobutane and at least a portion of the isobutane obtained by isomerization is reacted with linear olefins in an alkylation plant to produce an alkylate suitable for use as a gasoline blending component.
The alcohol fed to the etheration zone for reaction with the tertiary olefins in accordance with the process of the present invention can be one or a mixture of alcohols ranging from C alcohols up to high alcohols such as C alcohols. However, it is preferred that the alcohol or alcohol mixture fed to the etheration zone be a lower alcohol such as methanol up to about the amyl alcohols. It is particularly preferred in the process of the present invention to feed methanol to the etheration zone. Methanol is a relatively inexpensive alcohol and we have also determined that methanol can be produced in an over-all refinery combination process including the basic steps of the present invention. As is discussed in more detail hereinbelow, one of the important advantages of the present invention is its versatility and ability to combine with other refinery process steps. The methanol feed to the process of the present invention can be obtained from a combination hydrogen-methanol production plant with the hydrogen produced in the combined hydrogen-methanol plant being used in a hydrocracking plant, which hydrocracking plant in turn supplies at least a portion of the isobutane for reaction in the alkylation step according to the present invention.
The light hydrocarbon mixture fed to etheration zone 3 preferably boils between about propylene and 400F. More preferably, the light hydrocarbon stream comprises hydrocarbons within the range of about C to C The hydrocarbon mixture fed to the etheration zone can be produced or obtained in a variety of ways. Different streams produced in a refinery, for example, can be combined to obtain the light hydrocarbon mixture for feeding to etheration zone 3. It is particularly preferred in the process of the present invention to feed an olefin-rich C -C stream from a hydrocarbon cracking process to etheration zone 3. The C -C stream from the cracking process can be a relatively pure olefin stream containing only a few tenths percent or so paraffins such as isobutane, or the C -C stream may contain substantial amounts of paraffins such as 5-50 weight percent paraffins. One of the important advantages of the present invention is that both the etheration and hydration steps in the present invention operate as serial separation steps, i.e., in the etheration zone, tertiary olefins are converted to ethers which ethers are then easily separated from the remaining olefins and paraffins compared to the difficulty in separating tertiary olefins directly from the linear olefins. And in hydration zone 6, the linear olefins are reacted with water to form alcohols, which alcohols are usually relatively easily separated from the remaining paraffins compared to the difficulty of separating the C -C paraffins from the C C linear olefins.
The preferred olefin-rich C -C stream for feeding to etheration zone 3 in the process of the present invention can be obtained, for example, from a light hydrocarbon cracking process or a cracking process applied to a relatively heavy hydrocarbon such as gas oil. The cracking process can be thermal or catalytic. Suitable cracking processes operated at cracking temperatures between about 900 and 1,200F are described in US. Pat. No. 3,482,952 at column 3, line 22 to line 46, which disclosure is incorporated by reference into the present specification. It is preferred to obtain the olefin-rich light hydrocarbon mixture for feeding to the etheration zone in the present invention from a catalytic cracking process such as a fluid catalytic cracking process applied to relatively heavy hydrocarbons such as gas oils.
The olefin-rich stream for feeding to the etheration zone can also be obtained from the catalytic dehydrogenation of paraffins; for example, from the catalytic dehydrogenation of butane one obtains normal butenes and isobutene. Similarly, these olefins can be used to supplement the olefin feed to the alkylation zone.
Although C -C olefin-rich streams are advantageous feedstocks for the etheration reaction in the process of the present invention, streams containing mostly C olefins are the most preferred feedstock for the etheration reaction in the process of the present invention. Preferably, the C olefin-rich feed stream is obtained by Distilling a C rich cut from the effluent from a hydrocarbon cracking process such as a fluid catalytic cracking process. The C olefin-rich cut is a particularly preferred feedstock for the etheration reaction in the process of the present invention because the isobutene in the C cut has a relatively high reaction rate with alcohols such as methanol to form ethers compared to the reaction rates of higher tertiary olefins with alcohols to form ethers. Furthermore, we have determined that the methyl t-butyl ether formed in reacting isobutene with methanol has relatively high octane blending numbers when blended with gasoline boiling range hydrocarbons. Still further, the olefin-rich C stream provides a relatively high concentration of olefins compared to wider cuts such as C -C olefin-rich hydrocarbon fractions and this higher concentration of olefins contributes to the efficiency of the process of the present invention. In the process of the present invention, unreacted linear olefins and paraffins are removed from the etheration zone and passed at least in part to the hydration reaction step of the present invention. The preferred olefin-rich C fraction provides a relatively high concentration of linear butenes for hydration to produce at least secondary butyl alcohol in the hydration step of the present invention. The secondary butyl alcohol has a relatively high blending octane number compared to higher secondary alcohols. Unreacted isobutane (iC and unreacted linear olefins withdrawn from the hydration reaction step in the process of the present invention are fed to an alkylation process to form a high octane gasoline boiling range alkylate.
As indicated above, preferably at least a portion of the paraffinic C feed for the process of the present invention is obtained from a hydrocracking process. Hydrocracking using Group VIB and/or Group VIII components on acidic supports such as silica-alumina produces substantial quantities of isobutane. The isobutane is advantageously reacted with linear olefins in an alkylation zone to form a high-octane, gasoline-boilingrange alkylate. Typically, the alkylate boils in the range of about C to 350F.
The hydrocracking or other hydroconversion step such as hydrotreating or hydrofining can advantageously be combined with fluid catalytic cracking to produce at least a portion of the feedstock for the catalytic cracking process. According to a preferred overall embodiment of the present invention, hydroconversion is used to provide at least a portion of the isobutane which is reacted with olefins to form an alkylate, and at least a portion of the effluent from the hydroconversion step is fed to a catalytic cracking process which provides at least a portion of the C olefins fed to the etheration step of the present invention, and preferably at least a portion of the ethers, alcohols and alkylate produced in the etheration, hydration and alkylation steps of the present invention are blended with at least a portion of the gasoline-boiling-range hydrocarbons produced in the hydroconversion and/or catalytic cracking steps.
According to one preferred alternate over-all process embodiment in accordance with the present invention, a process is provided for producing a gasoline blending stock which comprises (a) feeding an alcohol and a C C stream, containing at least tertiary olefins, linear olefins, isobutane, n-butane and isopentane, to an etheration zone, (b) reacting the alcohol with the tertiary olefins in the etheration zone to obtain an ether, (0) separating the ether from unreacted linear olefins and paraffins, (d) feeding water and the unreacted linear olefins and paraffins to a hydration zone, (e) reacting the water with at least a portion of the unreacted linear olefins in the hydration zone and withdrawing at least a secondary alcohol and unreacted paraffins and olefins from the hydration zone, (f) separating the secondary alcohols from the unreacted paraffins and olefins, (g) feeding at least a portion of the unreacted olefins and paraffins to an alkylation plant for reaction to obtain an alkylate, and (h) blending at least portions of the ether, product alcohol and alkylate to produce a gasoline blending stock.
The gasoline blending stock produced in accordance with the present invention can be blended with various gasoline-boiling-range hydrocarbons to obtain an unleaded, relatively high-octane gasoline.
BRIEF DESCRIPTION OF THE DRAWING The drawing is a schematic process flow diagram illustrating one preferred embodiment of the process of the present invention.
DETAILED DESCRIPTION OF THE DRAWING Referring now more particularly to the drawing, a hydrocarbon mixture containing tertiary olefins, linear olefins, and isobutane is fed via line 1 to etheration zone 3. In etheration zone 3, the tertiary olefins are reacted with alcohol fed via line 2 to obtain an ether which is withdrawn from the etheration zone via line 4. It is, of course, to be understood that distillation facilities will be operated in conjunction with the etheration reactor in etheration zone 3.
To catalyze the ether synthesis reaction in zone 3, solid acidic or homogeneous acidic catalysts can be used. Preferred temperatures for use in the ether synthesis reactor are between and 225F and preferred pressures are between 10 and 600 psig. Preferred catalysts for use in the ether synthesis reactor are relatively high-molecular-weight, water-insoluble, carbonaceous materials containing at least one SO I-I group as the functional'group. These catalysts are exemplified by the sulfonated coals (Zeo-Karb H, Nalcite X, and Nalcite AX") produced by the treatment of bituminous coals with sulfuric acid and commercially marketed as zeolitic water softeners or base exchangers. These materials are usually available in a neutralized form and, in this case, must be activated to the hydrogen form by treatment with a mineral acid, such as hydrochloric acid, and water washed to remove sodium and chloride ions prior to use. Also suitable are the sulfonated resin type catalysts which include the reaction products of phenolformaldehyde resins with sulfuric acid (Amberlite IR-l, Amberlite IR-lOO, and Nalcite MX). Also useful are the sulfonated resinous polymers of coumarone indene with cyclopentadiene, sulfonated polymers of coumarone indene with furfural, sulfonated polymers of coumarone indene with cyclopentadiene and furfural, and sulfonated polymers of cyclopentadiene with furfural. The most preferred cationic exchange resins are strongly acidic exchange resins consisting essentially of sulfonated polystyrene resin, for instance a divinylbenzene cross-linked polystyrene matrix having about 0.5 to 20 percent, preferably about 4 to 16 percent, of copolymerized divinylbenzene therein to which are'attached ionizable or functional nuclear sulfonic acid groups. These resins are manufactured and sold commercially under various trade names; e.g., Dowex 50, Nalcite HCR, and Amberlyst 15. As commercially obtained, they have solvent contents of about 50 percent and can be used in the instant process in this form or can be dried and then used.
Particularly preferred as a catalyst for use in the ether synthesis zone is Amberlyst 15, which is a divinylbenzene cross-liked polystyrene matrix, having between O.52O percent of copolymerized divinylbenzene by weight of the resin catalyst to which is attached sulfonate groups, and having a macroreticular structure. More specifically, Amberlyst has the following properties:
As can be seen from the properties given above, Amberlyst 15 is generally obtained with a hydrogen ion concentration ('SO H concentration) of about 4.9 meq. per gram of catalyst.
The term macroreticular is used herein to connote a resin catalyst pore structure having a high degree of true porosity, that is, pores which are rigid and fixed within the resin beads. The high porosity gives rise to a large surface area which is conducive to high catalytic activity. The macroreticular structure in Amberlyst l5 permits ready access of reactants to the sulfonate groups or ions present throughout the resin catalyst beads. This accessibility is not generally found in conventional ion-exchange resins.
The olefin hydration in zone 6 can be catalyzed by mildly acidic solid catalysts or homogeneous acidic catalysts. Preferred temperatures for the hydration of olefins in hydration zone 6 are between about 70 and 325F and preferred pressures are between about 50 and 500 psig. Preferred catalysts for use in the hydration zone include those mentioned above for use in the ether synthesis zone, but somewhat reduced acidity is preferred for the hydration catalysts compared to the ether synthesis catalyst. Thus, Amberlyst 15 with the acidity adjusted to between about 0.5 and 2.5 meq. H+/g. of catalyst is a particularly preferred catalyst for use in the hydration zone.
Distillation facilities are an included part of hydration zone 6. In the distillation facilities, unreacted paraffins and olefins are separated from the secondary alcohol. The unreacted olefins, isobutane and other paraffins such as normal butane and isopentane are fed to distillation column 11.
According to a preferred embodiment of the present invention, additional butanes are also fed to distillation column 11 as indicated by line 10 in the drawing. Isopentane and, in general, hydrocarbons with less volatility than normal butane, are fractionated downward in Appearance Hard, spherical, dark-brown particles, toluene-saturated Typical particle size distribution, percent retained on:
16 mesh U.S. Standard Screens 2.4 16 20 mesh U.S. Standard Screens 24.2 20 30 mesh U.S. Standard Screens 47.9 -30 mesh U.S. Standard Screens 18.8 40 mesh U.S. Standard Screens 5.7 Through 50 mesh, percent 1.0 max. Whole bead content, 100 Bulk density, g/l as supplied 850 lbs/cu. ft. 54 True density, g/ml as supplied 1.4 Moisture, by weight less than 1% Solids, 55 Percentage swelling from dry state to solvent-saturated state hexane l2 toluene l5 ethylene dichloride l7 ethyl acetate 35 ethyl alcohol 66 water 66 Hydrogen ion concentration meq./g. dry 4.9 meq./ml. packed column 2.4 Surface Area, m /g. 40 50 Porosity, ml. pore/ml. bead .30 .35 Average Pore Diameter, A. 200 600 distillation column 11. An isopentane-rich stream is withdrawn from the bottom of the distillation column via line 12. This isopentane-rich stream is advantageously used as a gasoline blending component, as isopentane itself has a relatively high octane number.
A side-stream rich in normal butane is preferably withdrawn from the upper part of the distillation column as a liquid draw from a sump tray or the like at some position intermediate between the top of the column and the feed point to the column, or a normal butane-rich stream can be withdrawn from the lower part of the distillation column as a vapor side stream withdraw. In accordance with a preferred embodiment of the present invention, the normal butane is isomerized in C isomerization zone 14 to produce additional butane. The isomerization of normal butane in zone 14 can be carried out using, for example, a platinum on silica-alumina or platinum on chlorided alumina catalyst. Preferred operating temperatures for the normal butane isomerization are between about 200 and 750F and preferred pressures are between about 100 and 1,000 psig. In a typical normal butane isomerization process, a deisobutanizer is operated in conjunction with the isomerization reactor. However, in the process of the present invention, it is preferred to use distillation column 11 in conjunction with C isomerization zone 14 rather than to use a separate deisobutanizer column to further purify the normal butane feed passed via line 13 to zone 14. Zone 14 will, however, contain some separating and heating equipment operating in conjunction with the normal butane isomerization reactor. A typical normal butane isomerization process is described in the Oil and Gas Journal, Volume 56, No. 13, Mar. 31, 1958, at pages 73-76.
The normal butane feed to zone 14 is largely converted to isobutane which is withdrawn from zone 14 via line 15 and fed to distillation column 11 via line 16 and 9. Isobutane and unreacted olefins are distilled overhead in distillation column 11 and are withdrawn via line 17. The isobutane/olefin-rich stream withdrawn via line 17 is fed to alkylation zone 18 wherein the unreacted light olefms from the hydration step and/or the etheration step are introduced to the alkylation zone 18 via line 17. Additional olefins or paraffins from other sources can be added to the alkylation zone to adjust the olefin-paraffin ratio for most operation of an alkylation zone.
The alkylate produced in zone 18 is withdrawn via line 19 and preferably is blended with ethers and alcohols withdrawn from zones 3 and 6, respectively, to produce a relatively high-octane gasoline blending component in line 20. Although any one or more of the respective ether, secondary alcohol and alkylate streams produced in the present invention can advantageously be used as gasoline blending components, it is preferred to use a mixture of these components as a high-octane gasoline blending stock. In accordance with an alternate embodiment of the present invention, a portion of the alcohol, such as methanol, fed to the process of the present invention via line 2, is passed via line 21 for blending with one or more of the ether, alcohol or alkylate streams produced in accordance with the process of the present invention. In this instance, the product gasoline blending stock is withdrawn from the process via line 22.
A preferred embodiment of the present invention would operate as follows: A mixed hydrocarbon stream containing, for example, mostly C hydrocarbons such as isobutane, normal butane, isobutene and normal butene is fed to etheration zone 3 via line 1. The isobutene is reacted with methanol introduced to zone 3 via line 2 to produce tertiary butyl methyl ether. Also, a portion of the isobutene is reacted in etheration zone 3 with isopropyl alcohol to produce tertiary butyl isopropyl ether, which is a particularly good high-octane gasoline blending component. The isopropyl alcohol is produced in hydration zone 6 from propylene introduced as a separate stream to hydration zone 6. However, according to a preferred embodiment of the present invention, propylene contained in the mixed hydrocarbon feed to etheration zone 3 is used as the reactant to form isopropyl alcohol in hydration zone 6. Because the propylene does not contain a tertiary carbon atom, it does not react to form an ether to any appreciable extent in etheration zone 3, and thus etheration zone 3 serves to increase the linear olefin (including propylene) content of the mixed hydrocarbon stream originally fed to the etheration zone.
Thus, unreacted linear olefins in the effluent from the etheration zone are passed to hydration zone 6 wherein at least a portion is reacted with water to form secondary butyl alcohol, including isopropyl alcohol in those instances when propylene is present in the mixed hydrocarbon feed to the etheration zone.
A portion of the linear olefins in the effluent from the etheration zone and/or hydration zone are fed to an alkylation process to form a high-octane, gasolineboiling-range alkylate. The alkylation zone is operated in accordance with various wellknown alkylation processes including I-IF alkylation and H alkylation. It is to be understood that alkylation zone 18 includes distillation facilities so that an alkylate may be withdrawn from the alkylation zone via line 21. The isobutane fed to the alkylation step can be obtained directly as an outside isobutane stream, but preferably the isobutane is obtained in part from unreacted isobutane present in the effluent from the hydration zone and in part by nC, isomerization to increase the IQ, content of a mixed butane stream.
Thus, the oxygenated components which are produced in this embodiment of the present invention include tertiary butyl methyl ether, tertiary butyl isopropyl ether, isopropyl alcohol, and secondary butyl alcohol. One or more of these relatively high octane gasoline blending components can be blended with the alkylate produced in accordance with this preferred embodiment of the present invention to obtain a highoctane unleaded gasoline.
In another alternative embodiment, distillation column 11 is used to separate only the isopentanes and the remaining olefins and paraffins, including normal butane, are fed to alkylation zone 18. The normal butane will not react in the alkylation zone and is then separated from the alkylate and fed to isomerization zone 14. Separation of the normal butane from the alkylate is readily accomplished in a distillation column.
Although various embodiments of the invention have been described it is to be understood that they are meant to be illustrative only and not limiting. Certain features may be changed without departing from the spirit or scope of the invention. It is apparent that the present invention has broad application to the production of gasoline blending stocks in a combination process involving etheration, hydration, and alkylation.
Accordingly, the invention is not to be construed as limited to the specific embodiments or examples discussed but only as defined in the appended claims.
What is claimed is:
1. A process for producing a gasoline blending stock which comprises:
a. feeding an alcohol and a light hydrocarbon mixture containing at least tertiary olefins, linear olefins and isobutane to an etheration zone,
b. reacting the alcohol with the tertiary olefins in the etheration zone to obtain an ether and unreacted linear olefins and isobutane,
c. separating the ether from the linear olefins and isobutane,
d. feeding water and at least a portion of the linear olefins to a hydration zone,
e. reacting the water with the linear olefins in the hydration zone to obtain a product alcohol,
f. separating unreacted olefins and paraffins from the secondary alcohol,
g. feeding at least a portion of the unreacted olefins and paraffins to an alkylation plant for reaction to obtain an alkylate, and
h. blending at least portions of the ether, product alcohol and alkylate to produce a gasoline blending stock.
2. A process in accordance with claim 1 wherein both the isobutane and linear olefins are fed to the hydration zone and unreacted isobutane and linear olefins are withdrawn from the hydration zone and are fed to an alkylation plant for reaction to form an alkylate.
3. A process in accordance with claim 1 wherein the light hydrocarbon mixture also contains n-butane and the n-butane is isomerized to obtain isobutane and at least a portion of the isobutane obtained by isomerization is combined with olefins in an alkylation zone to form an alkylate.
4. A process in accordance with claim 1 wherein the light hydrocarbon mixture comprises C -C hydrocarbons obtained from a hydrocarbon cracking process.
5. A process in accordance with claim 4 wherein the C -C hydrocarbons are obtained from fluid catalytic cracking.
6. A process for producing a gasoline blending stock which comprises:
a. feeding an alcohol and a C -C cracking effluent stream, containing at least tertiary olefins, linear olefins, isobutane, n-butane and isopentane, to an etheration zone,
b. reacting the alcohol with the tertiary olefins in the etheration zone to obtain an ether,
c. separating the ether from unreacted linear olefins and paraffins,
d. feeding water and the unreacted linear olefins and paraffins to a hydration zone,
6. reacting the water with the unreacted linear olefins in the hydration zone and withdrawing a product alcohol and unreacted paraffins from the hydration zone,
f. separating unreacted olefins and paraffins from the secondary alcohol,
g. feeding at least a portion of the unreacted olefins and paraffins to an alkylation plant for reaction to obtain an alkylate, and
h. blending at least portions of the ethers, product alcohol and alkylate to produce a gasoline blending stock.
7. The process of claim 6 wherein isopropyl alcohol is produced in said hydration zone by the addition of propylene to said hydration zone.
8. The process of claim 7 wherein a portion of said isopropyl alcohol is recycled to said etheration zone.

Claims (8)

1. A PROCESS FOR PRODUCING A GASOLINE BLENDING STOCK WHICH COMPRISES: A. FEEDING AN ALCOHOL AND A LIGHT HYDROCARBON MIXTURE CONTAINING AT LEAST TERTIARY OLEFINS, LINEAR OLEFINS AND ISOBUTANE TO AN ETHERATION ZONE B. REACTING THE ALCOHOL WITH THE TERTIARY OLEFINS IN THE ETHERATION ZONE TO OBTAIN AN ETHER AND UNREACTED LINEAR OLEFINS AND ISOBUTANE. C. SEPARATING THE ETHER FROM THE LINEAR OLEFINS AND ISOBUTANE, D. FEEDING WATER AND AT LEAST A PORTION OF THE LINEAR OLEFINS TO A HYDRATION ZONE, E. REACTING THE WATER WITH THE LINEAR OLEFINS IN THE HYDRATION ZONE TO OBTAIN A PRODUCT ALCOHOL F. SEPARATING UNREACTED OLEFINS AND PARAFFINS FROM THE SECONDARY ALCOHOL, G. FEEDING AT LEAST A PORTION OF THE UNREACTED OLEFINS AND PARAFFINS TO AN ALKYLATION PLANT FOR REACTION TO OBTAIN AN ALKYLATE, AND H. BLENDING AT LEAST PORTION OF THE ETHER, PRODUCT ALCOHOL AND ALKYLATE TO PRODUCE A GASOLINE BLENDING STOCK.
2. A process in accordance with claim 1 wherein both the isobutane and linear olefins are fed to the hydration zone and unreacted isobutane and linear olefins are withdrawn from the hydration zone and are fed to an alkylation plant for reaction to form an alkylate.
3. A process in accordance with claim 1 wherein the light hydrocarbon mixture also contains n-butane and the n-butane is isomerized to obtain isobutane and at least a portion of the isobutane obtained by isomerization is combined with olefins in an alkylation zone to form an alkylate.
4. A process in accordance with claim 1 wherein the light hydrocarbon mixture comprises C4-C5 hydrocarbons obtained from a hydrocarbon cracking process.
5. A process in accordance with claim 4 wherein the C4-C5 hydrocarbons are obtained from fluid catalytic cracking.
6. A process for producing a gasoline blending stock which comprises: a. feeding an alcohol and a C4-C5 cracking effluent stream, containing at least tertiary olefins, linear olefins, isobutane, n-butane and isopentane, to an etheration zone, b. reacting the alcohol with the tertiary olefins in the etheration zone to obtain an ether, c. separating the ether from unreacted linear olefins and paraffins, d. feeding water and the unreacted linear olefins and paraffins to a hydration zone, e. reacting the water with the unreacted linear olefins in the hydration zone and withdrawing a product alcohol and unreacted paraffins from the hydration zone, f. separating unreacted olefins and paraffins from the secondary alcohol, g. feeding at least a portion of the unreacted olefins and paraffins to an alkylation plant for reaction to obtain an alkylate, and h. blending at least portions of the ethers, product alcohol and alkylate to produce a gasoline blending stock.
7. The process of claim 6 wherein isopropyl alcohol is produced in said hydration zone by the addition of propylene to said hydration zone.
8. The process of claim 7 wherein a portion of said isopropyl alcohol is recycled to said etheration zone.
US518140A 1970-06-26 1974-10-25 Hydrocarbon conversion process Expired - Lifetime US3912463A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US518140A US3912463A (en) 1970-06-26 1974-10-25 Hydrocarbon conversion process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US00050123A US3849082A (en) 1970-06-26 1970-06-26 Hydrocarbon conversion process
US518140A US3912463A (en) 1970-06-26 1974-10-25 Hydrocarbon conversion process

Publications (1)

Publication Number Publication Date
US3912463A true US3912463A (en) 1975-10-14

Family

ID=26727909

Family Applications (1)

Application Number Title Priority Date Filing Date
US518140A Expired - Lifetime US3912463A (en) 1970-06-26 1974-10-25 Hydrocarbon conversion process

Country Status (1)

Country Link
US (1) US3912463A (en)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118425A (en) * 1975-06-06 1978-10-03 Texaco Inc. Method for preparation of ethers
US4178154A (en) * 1975-02-05 1979-12-11 Henri Rothlisberger Light synthetic fuel
US4204077A (en) * 1978-10-02 1980-05-20 Gulf Canada Limited Etherification processing of light hydrocarbons
US4270929A (en) * 1978-08-31 1981-06-02 Institut Francais Du Petrole Process for producing gasoline of high octane number, in particular lead-free gasoline
US4299999A (en) * 1979-05-09 1981-11-10 Institut Francais Du Petrole Process for the preparation and isolation of methyl-tert-butyl ether
US4329516A (en) * 1979-05-28 1982-05-11 Davy International Aktiengesellschaft Process for the production of methyl t-butyl ether
US4334890A (en) * 1981-02-03 1982-06-15 The Halcon Sd Group, Inc. Process for gasoline blending stocks
US4356001A (en) * 1980-06-02 1982-10-26 Texaco Inc. Method of extending hydrocarbon fuels including gasolines and fuels heavier than gasoline
US4393250A (en) * 1981-04-28 1983-07-12 Veba Oel Ag Process for producing alcohols and ethers
US4408085A (en) * 1981-04-28 1983-10-04 Veba Oel Ag Process for preparing sec-butyl alcohol and sec-butyl tert-butyl ether
US4479018A (en) * 1981-08-28 1984-10-23 Phillips Petroleum Company Combined ether and alkylate production
US4581474A (en) * 1985-03-11 1986-04-08 Phillips Petroleum Company Hydrocarbon conversion process
US4731489A (en) * 1986-07-18 1988-03-15 Conoco Inc. Process for production of gasoline blending stock
US4797133A (en) * 1986-12-29 1989-01-10 Uop Inc. Process for recovery of butene-1 from mixed C4 hydrocarbons
US4830635A (en) * 1987-12-08 1989-05-16 Mobil Oil Corporation Production of liquid hydrocarbon and ether mixtures
US4859210A (en) * 1987-01-08 1989-08-22 Basf Aktiengesellschaft Motor fuel or lubricant composition containing polybutyl or polyisobutyl derivatives
US4925455A (en) * 1989-03-17 1990-05-15 Mobil Oil Corporation Process for the etherification of linear and branched olefins
US4988366A (en) * 1989-10-24 1991-01-29 Mobil Oil Corporation High conversion TAME and MTBE production process
US5013329A (en) * 1989-03-31 1991-05-07 Mobil Oil Corporation Conversion of light hydrocarbons to ether rich gasoline
US5080691A (en) * 1990-04-04 1992-01-14 Mobil Oil Corp. Process for the conversion of light olefins to ether-rich gasoline
EP0505843A1 (en) * 1991-03-15 1992-09-30 Phillips Petroleum Company Integrated olefin processing
US5233101A (en) * 1992-10-09 1993-08-03 Mobil Oil Corporation Fluidized catalyst process for production and hydration of olefins
US5413717A (en) * 1993-08-30 1995-05-09 Texaco Inc. Method of recovering MTBE from wastewater
US20060162421A1 (en) * 2005-01-21 2006-07-27 Brady Worldwide, Inc. Shock indicator
CN110945109A (en) * 2017-07-27 2020-03-31 沙特基础工业全球技术有限公司 Method for producing fuel additive
CN112041291A (en) * 2018-05-07 2020-12-04 沙特基础工业全球技术有限公司 Method for producing fuel oil additive
US11161796B2 (en) 2018-09-18 2021-11-02 Sabic Global Technologies B.V. Systems and processes for efficient production of one or more fuel additives
US11248181B2 (en) 2018-04-19 2022-02-15 Sabic Global Technologies B.V. Method of producing a fuel additive
US11414611B2 (en) 2018-05-07 2022-08-16 Sabic Global Technologies B.V. Method of producing a fuel additive
US11427518B2 (en) 2018-03-19 2022-08-30 Saudi Arabian Oil Company Method of producing a fuel additive
US11518951B2 (en) 2018-03-19 2022-12-06 Sabic Global Technologies B.V. Method of producing a fuel additive
US11697626B2 (en) * 2018-05-18 2023-07-11 Sabic Global Technologies B.V. Method of producing a fuel additive with a hydration unit

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2118881A (en) * 1934-03-09 1938-05-31 Socony Vacuum Oil Co Inc Manufacture of alcohols
US2827500A (en) * 1954-10-14 1958-03-18 Exxon Research Engineering Co Integrated hydration and alkylation of gaseous olefins
US2952612A (en) * 1957-06-27 1960-09-13 Shell Oil Co Production of high octane motor fuel with an alkyl ether additive
US3007782A (en) * 1958-07-31 1961-11-07 Standard Oil Co Motor fuel composition
US3224848A (en) * 1959-03-16 1965-12-21 Shell Oil Co Gasoline composition
US3482952A (en) * 1968-04-29 1969-12-09 Chevron Res Process for production of gasoline
US3530060A (en) * 1968-12-30 1970-09-22 Mobil Oil Corp Gasoline manufacture

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2118881A (en) * 1934-03-09 1938-05-31 Socony Vacuum Oil Co Inc Manufacture of alcohols
US2827500A (en) * 1954-10-14 1958-03-18 Exxon Research Engineering Co Integrated hydration and alkylation of gaseous olefins
US2952612A (en) * 1957-06-27 1960-09-13 Shell Oil Co Production of high octane motor fuel with an alkyl ether additive
US3007782A (en) * 1958-07-31 1961-11-07 Standard Oil Co Motor fuel composition
US3224848A (en) * 1959-03-16 1965-12-21 Shell Oil Co Gasoline composition
US3482952A (en) * 1968-04-29 1969-12-09 Chevron Res Process for production of gasoline
US3530060A (en) * 1968-12-30 1970-09-22 Mobil Oil Corp Gasoline manufacture

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4178154A (en) * 1975-02-05 1979-12-11 Henri Rothlisberger Light synthetic fuel
US4118425A (en) * 1975-06-06 1978-10-03 Texaco Inc. Method for preparation of ethers
US4270929A (en) * 1978-08-31 1981-06-02 Institut Francais Du Petrole Process for producing gasoline of high octane number, in particular lead-free gasoline
US4204077A (en) * 1978-10-02 1980-05-20 Gulf Canada Limited Etherification processing of light hydrocarbons
US4299999A (en) * 1979-05-09 1981-11-10 Institut Francais Du Petrole Process for the preparation and isolation of methyl-tert-butyl ether
US4329516A (en) * 1979-05-28 1982-05-11 Davy International Aktiengesellschaft Process for the production of methyl t-butyl ether
US4356001A (en) * 1980-06-02 1982-10-26 Texaco Inc. Method of extending hydrocarbon fuels including gasolines and fuels heavier than gasoline
US4334890A (en) * 1981-02-03 1982-06-15 The Halcon Sd Group, Inc. Process for gasoline blending stocks
US4393250A (en) * 1981-04-28 1983-07-12 Veba Oel Ag Process for producing alcohols and ethers
US4408085A (en) * 1981-04-28 1983-10-04 Veba Oel Ag Process for preparing sec-butyl alcohol and sec-butyl tert-butyl ether
US4479018A (en) * 1981-08-28 1984-10-23 Phillips Petroleum Company Combined ether and alkylate production
US4581474A (en) * 1985-03-11 1986-04-08 Phillips Petroleum Company Hydrocarbon conversion process
US4731489A (en) * 1986-07-18 1988-03-15 Conoco Inc. Process for production of gasoline blending stock
US4797133A (en) * 1986-12-29 1989-01-10 Uop Inc. Process for recovery of butene-1 from mixed C4 hydrocarbons
US4859210A (en) * 1987-01-08 1989-08-22 Basf Aktiengesellschaft Motor fuel or lubricant composition containing polybutyl or polyisobutyl derivatives
US4830635A (en) * 1987-12-08 1989-05-16 Mobil Oil Corporation Production of liquid hydrocarbon and ether mixtures
US4925455A (en) * 1989-03-17 1990-05-15 Mobil Oil Corporation Process for the etherification of linear and branched olefins
US5013329A (en) * 1989-03-31 1991-05-07 Mobil Oil Corporation Conversion of light hydrocarbons to ether rich gasoline
US4988366A (en) * 1989-10-24 1991-01-29 Mobil Oil Corporation High conversion TAME and MTBE production process
US5080691A (en) * 1990-04-04 1992-01-14 Mobil Oil Corp. Process for the conversion of light olefins to ether-rich gasoline
EP0505843A1 (en) * 1991-03-15 1992-09-30 Phillips Petroleum Company Integrated olefin processing
AU636525B2 (en) * 1991-03-15 1993-04-29 Phillips Petroleum Company Process for producing gasoline blending components
US5233101A (en) * 1992-10-09 1993-08-03 Mobil Oil Corporation Fluidized catalyst process for production and hydration of olefins
US5413717A (en) * 1993-08-30 1995-05-09 Texaco Inc. Method of recovering MTBE from wastewater
US20060162421A1 (en) * 2005-01-21 2006-07-27 Brady Worldwide, Inc. Shock indicator
KR20200035400A (en) * 2017-07-27 2020-04-03 사빅 글로벌 테크놀러지스 비.브이. Method for manufacturing fuel additives
CN110945109A (en) * 2017-07-27 2020-03-31 沙特基础工业全球技术有限公司 Method for producing fuel additive
US11613717B2 (en) 2017-07-27 2023-03-28 Sabic Global Technologies B.V. Method of producing a fuel additive
US11427518B2 (en) 2018-03-19 2022-08-30 Saudi Arabian Oil Company Method of producing a fuel additive
US11518951B2 (en) 2018-03-19 2022-12-06 Sabic Global Technologies B.V. Method of producing a fuel additive
US11248181B2 (en) 2018-04-19 2022-02-15 Sabic Global Technologies B.V. Method of producing a fuel additive
CN112041291A (en) * 2018-05-07 2020-12-04 沙特基础工业全球技术有限公司 Method for producing fuel oil additive
US11407952B2 (en) 2018-05-07 2022-08-09 Saudi Arabian Oil Company Method of producing a fuel additive
US11414611B2 (en) 2018-05-07 2022-08-16 Sabic Global Technologies B.V. Method of producing a fuel additive
CN112041291B (en) * 2018-05-07 2023-10-20 沙特基础工业全球技术有限公司 Method for producing fuel additive
US11697626B2 (en) * 2018-05-18 2023-07-11 Sabic Global Technologies B.V. Method of producing a fuel additive with a hydration unit
US11161796B2 (en) 2018-09-18 2021-11-02 Sabic Global Technologies B.V. Systems and processes for efficient production of one or more fuel additives

Similar Documents

Publication Publication Date Title
US3912463A (en) Hydrocarbon conversion process
US3849082A (en) Hydrocarbon conversion process
US3846088A (en) Process of drying ethers
Ancillotti et al. Oxygenate fuels: Market expansion and catalytic aspect of synthesis
US4423251A (en) Process employing sequential isobutylene hydration and etherification
US4118425A (en) Method for preparation of ethers
US5254790A (en) Integrated process for producing motor fuels
US3726942A (en) Production of gasoline components including 2-methyl-2-methoxypropane
US4886925A (en) Olefins interconversion and etherification process
US4270929A (en) Process for producing gasoline of high octane number, in particular lead-free gasoline
US4252541A (en) Method for preparation of ethers
BR0104555B1 (en) process for the preparation of highly pure refined ii and methyl tert-butyl ether and their uses.
US3482952A (en) Process for production of gasoline
US5047070A (en) Integrated process for production of gasoline and ether from alcohol with feedstock extraction
US5171331A (en) Process for producing gasoline
JP2833721B2 (en) Method for producing high octane, low olefin motor fuel and motor fuel component
US3904384A (en) Gasoline production
US4316724A (en) Gasoline and alcohol blends
EP0474188A2 (en) Methyl-tertiaryalkyl ether production
US3903251A (en) Gasoline production
CN1046549A (en) The etherification technology method of olefine contained gasoline
EP0514593A1 (en) Production of ether from alcohol and isoolefin in the presence of H2O with H2O/alcohol recycle
JPS6133877B2 (en)
Kiatkittipong et al. Simultaneous enhancement of ethanol supplement in gasoline and its quality improvement
US4046520A (en) Gasoline production