US3816294A - Production of alkylate - Google Patents

Production of alkylate Download PDF

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Publication number
US3816294A
US3816294A US00319573A US31957372A US3816294A US 3816294 A US3816294 A US 3816294A US 00319573 A US00319573 A US 00319573A US 31957372 A US31957372 A US 31957372A US 3816294 A US3816294 A US 3816294A
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US
United States
Prior art keywords
stream
stream containing
charge
preparing
alkylate gasoline
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
US00319573A
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English (en)
Inventor
R Wilson
J Estes
S Kravitz
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Texaco Inc
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Texaco Inc
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
Application filed by Texaco Inc filed Critical Texaco Inc
Priority to US00319573A priority Critical patent/US3816294A/en
Priority to JP48108611A priority patent/JPS4999503A/ja
Priority to GB5125473A priority patent/GB1393044A/en
Priority to CA186,333A priority patent/CA1002895A/en
Priority to NL7316114A priority patent/NL7316114A/xx
Priority to SE7316088A priority patent/SE384872B/xx
Priority to BE138455A priority patent/BE808149A/xx
Priority to DE2360980A priority patent/DE2360980A1/de
Priority to FR7343964A priority patent/FR2212419B3/fr
Priority to IT32286/73A priority patent/IT1002359B/it
Application granted granted Critical
Publication of US3816294A publication Critical patent/US3816294A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the method of this invention for preparing a product stream containing alkylate gasoline from a charge stream containing paraffinic components may comprise passing said charge stream into contact with an.
  • isomerizing-cracking catalyst at isomerizing-cracking conditions in the presence of hydrogen thereby forming an isomerized-cracked stream containing isobutane and light and heavy paraffins;
  • paraffinic gasoline blending components which may be treated by the process of this invention may typically be a stream which is available in a refinery. Most commonly it will be a stream containing light paraffinic components. Typical of such streams are those containing predominantly lower paraffins including butanes, pentanes, etc. and illustrative of such streams are light straight run products, various condensates, and raffinates from which aromatics have been extracted.
  • the charge may be a pure C or C paraffin, it more commonly may be a mixture containing C to C paraffins.
  • the paraffin content may be 60-100 percent, preferably 70-90 percent, say about 80 percent.
  • the charge may also contain naphthenes in amount of 5-30 percent, preferably 5-20 percent, say 8 percent,
  • aromatics in amount of 2-15 percent, say 12 percent. Lesser amounts of other components may be present including aromatics, etc.
  • octane rating (RON Clear) of the charge may be less than about 60, typically 30-50, say 45
  • a typical charge stream may be a light Udex raffinate (from which the aromatics have been extracted) having the following composition:
  • This distillate may have a (RON Clear) octane number of 60.8, an IBP of 92F, an EBP of 300F, and a gravity of 79.2API.
  • the charge stream containing paraffinic components may be passed to an isomerizing-cracking operation wherein it is subjected to contact with an isomerizingcracking catalyst at isomerizing-cracking conditions to form an isomerized-cracked stream containing isobutane, light paraffins, and heavy paraffins.
  • the isomerizing-cracking catalyst is a catalyst which is characterized by its ability to crack hydrocarbons, preferably eg a charge containing paraffins, typically in the C to C range, to a product containing typically C and C paraffins and to simultaneously isomerize the product and/or the charge to permit formation of substantial quantities of isobutane e. g. as by isomerization of butane.
  • a typical catalyst may be an activated alumina such as that prepared by the process disclosed in US. Pat. No. 3,689,434 which issued to Robert M. Suggitt, John H. Estes, and Stanley Kravitz assigned to Texaco Inc. (Also useful may be the catalysts disclosed in US. Pat. Nos. 3,607,959 and 3,567,796 and 3,523,142 all assigned to the same assignee).
  • the catalysts of that patent may be prepared by contacting alumina with an activator system comprising (a) chlorine or bromine and (b) an inorganic sulfur compound which may be hydrogen sulfide or S, X, wherein m is 14 and X is chlorine or bromine. Activation is typically effected at 350F-750F.
  • the preferred ratio of chlorine or bromine to the inorganic sulfur compound may be 0.1:1 to 4:1; and the product catalyst may contain 3-15 percent (wt percent) chlorine or bromine.
  • the catalyst also contains 0.01-5 percent by weight of platinum, palladium, rhodium, or ruthemum.
  • a preferred catalyst may be that prepared by the process of experimental Example I of U.S. Pat. No. 3,689,434 a chlorided platinum on alumina catalyst.
  • lsomerization-cracking of the charge stream containing paraffinic components in practice of the process of this invention may be effected by passing 100 parts by volume (this number serving as a basis for the numbers that follow) in liquid phase (except for the hydrogen which is in the gas phase) at 300-400F, preferably 3l0F-375F, say 325F and pressure of 100-1000 psig, preferably 300-700 psig, say 300 psig to an isomerization-cracking operation.
  • hydrogen in amount of 0.1-5, preferably 0.2-3.0, say 1.5 moles per mole of hydrocarbon charge. This may correspond to a hydrogen rate of 300-l5,000, preferably (SOD-10,000, say 5,000 SCFB.
  • the hydrogen purity may be 50-100 percent, preferably 80-100 percent, say 95 percent by volume.
  • the space velocity (LHSV) of the total charge through the catalyst bed may be 0.5-8, preferably l-3, say 2.
  • paraffins may be converted to an isomerized-cracked product stream containing isobutane and light and heavy hydrocarbons.
  • the paraffins typically containing butane may be converted to a product containing iso-butane.
  • This product stream may be withdrawn and passed to a high pressure separator, wherein 50 100 parts, preferably 70 98 parts, say 95 parts of hydrogen may be flashed off at 300-700 psig, say 490 psig, and recirculated to the isomerization-cracking operation.
  • the product stream, from which hydrogen has been separated contains (a) light paraffins i.e. paraffins having boiling points lower than that of isobutane and including typically C and C (b) isobutane, and heavy paraffins i.e. paraffins having boiling points higher than that of isobutane and including n-butane, C and C
  • This product stream in the preferred embodiment may be passed to a fractionating or separating operation wherein light parafiins, isobutane, and heavy paraflins and hydrogen are separated; it is preferred however that the hydrogen be separated (at least in major portion thereof) prior to the fractionating operation in which the other three components may be separated.
  • the preferred fractionation product will include (a) a light paraffin stream, (b) an isobutane-containing stream, and (c) a heavy paraffin stream.
  • the mode of separation may depend upon the relative proportions of the various components. It may for example be desirable to effect fractionation in a first operation wherein an isobutane and lighter fraction is separated as overhead from a heavier bottom fraction, followed by a second fractionation operation in which isobutane bottoms are separated from a lighter second overhead fraction.
  • fractionation in a first step may yield as overhead a lighter fraction and as bottoms isobutane and a heavier fraction the latter bottoms being further fractionated to yield isobutane overhead and as second bottoms a heavier fraction.
  • separation may be carried out in a single fractionating tower yielding light paraffms as overhead, heavy paraffins as bottoms, and an isobutane fraction as a side-cut which latter is preferably stripped to yield a clean isobutane fraction.
  • the product streams, as recovered from separation may include the following:
  • the temperature of thermal steam cracking may be l,l00F-1,700F, preferably l,200F-l,600F, say 1,400F at 0-100 psig, preferably 3-50 psig, say 25 psig with a steam to hydrocarbon mole ratio of 01-10, preferably 0.2-8, say 5.
  • the thermally cracked product stream containing an olefin fraction may preferably be fractionally distilled to yield (a) a light olefinic distillate fraction, (b) a thermal naphtha fraction, and (c) a C to C olefin fraction.
  • 5-95 parts, preferably 15-85 parts, say 61.2 parts of the light olefinic distillate fraction may contain components having a boiling point below propylene.
  • this stream may contain the following (based on the charge to thermal cracking):
  • This C to C olefin stream in total amount of 5-45 parts, preferably 7-40 parts, say 12.4 parts is passed to an alkylation operation wherein it may be used to alkylate the isobutane-containing stream recovered from fractionation of the isomerized-cracked stream.
  • Alkylation may be effected at 40F-70F, preferably 45F-60F, say 55F in the presence of 85-98 percent, preferably 90-97 percent, say 95 percent sulfuric acid and at a space velocity (GPM butylene per gallon of acid in contactor) of 0. l-0.6, preferably 0.15-0.40, say 0.25.
  • the internal mole ratio of isobutane to olefin may be 100-700, preferably 150-550, say 250; and the external mole ratio may be 2-40, preferably 4-30, say 10.
  • the product alkylate gasoline fraction, recovered in total amount of 10-60 parts, preferably -50 parts, say 31.5 parts may be characterized by an octane (RON Clear) number of 91-102, say 95.0.
  • the product alkylate gasoline may be obtained in amount of 10-60 parts, preferably 15-50 parts, say 31.5 parts per 100 parts of charge to the initial isomerization-cracking operation.
  • This amount of gasoline may be increased by hydrogenation of the dripolene or thermal naphtha.
  • hydrogenation of this stream at 500F.-750F., preferably 525F.-725F, say 650F. and 100-1000 psig, preferably 150-800 psig, say 500 psig may be carried out over a nickel-molybdenum, on alumina catalyst such as that sold under the trademark American Cyamid HDS-3 catalyst.
  • the ratio of hydrogen to thermal naphtha may be ZOO-5,000 SCFB, preferably 300-2,000 SCFB say 1,000 SCFB; and the LHSV may be 0.2 10, preferably 0.4 8, say 2.0.
  • Product hydrogenated thermal naphtha (a gasoline cut), obtained in amount of 5-50 parts, preferably 7 40 parts, say 13.9 parts, may be characterized by the following:
  • the charge to the process in line 10 may include 10,000 BPD of light Udex Raffinate having a RON Clear octane number of 45 and containing 80.7 percent paraffins, 7.8 percent naphthenes, and 11.5 percent aromatics.
  • This charge in liquid phase is mixed with 5000 SCFB of pure hydrogen admitted through line 11; and the mixture is passed through line 12 to isomerizing-cracking operation 13.
  • the catalyst in operation 13 is that prepared in accordance with the experimental catalyst of Example I of US. Pat. No. 3,689,434 a chloride-activated plantinized alumina catalyst.
  • Conditions during operation 13 include a temperature of 325F, a pressure of 300 psig, and an LHSV of 2.
  • Effluent leaving through line 14 is passed through separation operation 15 at 325F. and 380 psig to yield a recycle stream of hydrogen which is withdrawn through line 11.
  • fractionation operation 17 Also withdrawn from separation operation 15, is the hydrogen-free stream in line 16; and this stream is passed to fractionation operation 17 schematically represented.
  • operation 17 there is separated an isobutane-containing stream, withdrawn through line 18 containing 2,330 BPD of isobutane.
  • a light paraffin stream withdrawn through line 19, containing principally propane (590 BPD) and nbutane (250 BPD) and a heavy paraffin stream, withdrawn through line 20, containing naphthenes and paraffins of heavier molecular weight than C, in amount of 6,830 BPD.
  • the light paraffin stream in line 19 and the heavy paraffin stream in line 20 are combined in line 21 and passed to thermal steam cracking operation 22 operated at 1,400F. and 25 psig with a steam to hydrocarbon mole ratio of 5.
  • charge stream is Component
  • the thermally cracked product containing an olefin fraction is fractionally distilled in operation 24 to yield a light olefinic distillate, containing ethylene as the main olefin, in amount of 61.2 parts (withdrawn through line 25) and a heavier thermal naphtha or dripolene withdrawn through line 26 in amount of 1,375 BPD.
  • This latter pentane plus stream is partially hydrogenated (with 1,000 SCFB of hydrogen admitted through line 27) at 650F and 500 psig in the presence of nickel-molybdenum on alumina (American Cyanamid HDS-3) hydrogenation catalyst in operation 28 and the hydrogenated naphtha, in amount of 1,390 BPD, passed through line 29 to the gasoline pool.
  • the product in line 29 has an octane (RON Clear) number of 98.0.
  • Alkylation is effected at 55F in the presence of 95 percent sulfuric acid at a space velocity of 0.25.
  • the internal mole ratio of isobutane to olefin is 250; and the external mole ratio is 10.
  • the product alkylate gasoline fraction, withdrawn through line 32 in amount of 3,150 BPD, is characterized by an octane number (RON Clear) of 95.0.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00319573A 1972-12-29 1972-12-29 Production of alkylate Expired - Lifetime US3816294A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US00319573A US3816294A (en) 1972-12-29 1972-12-29 Production of alkylate
JP48108611A JPS4999503A (enExample) 1972-12-29 1973-09-28
GB5125473A GB1393044A (en) 1972-12-29 1973-11-05 Production of alkylate
CA186,333A CA1002895A (en) 1972-12-29 1973-11-21 Production of alkylate
NL7316114A NL7316114A (enExample) 1972-12-29 1973-11-26
SE7316088A SE384872B (sv) 1972-12-29 1973-11-28 Sett att framstella alkylatbensin av en satsad produkt bestaende av paraffinkomponenter medelst isomerinering och krackning i nervaro av vete samt efterfoljande termisk krackning i nervaro av anga och alkylering
BE138455A BE808149A (fr) 1972-12-29 1973-12-03 Preparation d'un produit d'alkylation
DE2360980A DE2360980A1 (de) 1972-12-29 1973-12-07 Verfahren zur herstellung eines alkylatbenzins
FR7343964A FR2212419B3 (enExample) 1972-12-29 1973-12-10
IT32286/73A IT1002359B (it) 1972-12-29 1973-12-27 Metodo di preparazione di alchilati

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00319573A US3816294A (en) 1972-12-29 1972-12-29 Production of alkylate

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US3816294A true US3816294A (en) 1974-06-11

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US00319573A Expired - Lifetime US3816294A (en) 1972-12-29 1972-12-29 Production of alkylate

Country Status (10)

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US (1) US3816294A (enExample)
JP (1) JPS4999503A (enExample)
BE (1) BE808149A (enExample)
CA (1) CA1002895A (enExample)
DE (1) DE2360980A1 (enExample)
FR (1) FR2212419B3 (enExample)
GB (1) GB1393044A (enExample)
IT (1) IT1002359B (enExample)
NL (1) NL7316114A (enExample)
SE (1) SE384872B (enExample)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3922216A (en) * 1974-05-29 1975-11-25 Texaco Inc Production of light ends
US3928172A (en) * 1973-07-02 1975-12-23 Mobil Oil Corp Catalytic cracking of FCC gasoline and virgin naphtha
US4049539A (en) * 1975-06-13 1977-09-20 Mobil Oil Corporation Two-stage process for upgrading naphtha
US4097363A (en) * 1976-07-12 1978-06-27 Gulf Research & Development Company Thermal cracking of light gas oil at high severity to ethylene
US4118425A (en) * 1975-06-06 1978-10-03 Texaco Inc. Method for preparation of ethers
US4911823A (en) * 1984-12-27 1990-03-27 Mobil Oil Corporation Catalytic cracking of paraffinic feedstocks with zeolite beta
US6059956A (en) * 1994-10-07 2000-05-09 Europeene De Retraitment De Catalyseurs Eurecat Off-site pretreatment of a hydrocarbon treatment catalyst
US6153089A (en) * 1999-03-29 2000-11-28 Indian Oil Corporation Limited Upgradation of undesirable olefinic liquid hydrocarbon streams
US20160369188A1 (en) * 2013-07-02 2016-12-22 Thomas Hubertus Maria HOUSMANS Process for upgrading refinery heavy residues to petrochemicals
WO2020128156A1 (en) * 2018-12-17 2020-06-25 Neste Oyj Method to produce high quality components from renewable raw material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10995045B2 (en) * 2018-10-09 2021-05-04 Uop Llc Isomerization zone in alkylate complex

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928172A (en) * 1973-07-02 1975-12-23 Mobil Oil Corp Catalytic cracking of FCC gasoline and virgin naphtha
US3922216A (en) * 1974-05-29 1975-11-25 Texaco Inc Production of light ends
US4118425A (en) * 1975-06-06 1978-10-03 Texaco Inc. Method for preparation of ethers
US4049539A (en) * 1975-06-13 1977-09-20 Mobil Oil Corporation Two-stage process for upgrading naphtha
US4097363A (en) * 1976-07-12 1978-06-27 Gulf Research & Development Company Thermal cracking of light gas oil at high severity to ethylene
US4911823A (en) * 1984-12-27 1990-03-27 Mobil Oil Corporation Catalytic cracking of paraffinic feedstocks with zeolite beta
US6059956A (en) * 1994-10-07 2000-05-09 Europeene De Retraitment De Catalyseurs Eurecat Off-site pretreatment of a hydrocarbon treatment catalyst
US6153089A (en) * 1999-03-29 2000-11-28 Indian Oil Corporation Limited Upgradation of undesirable olefinic liquid hydrocarbon streams
US20160369188A1 (en) * 2013-07-02 2016-12-22 Thomas Hubertus Maria HOUSMANS Process for upgrading refinery heavy residues to petrochemicals
US20190062655A1 (en) * 2013-07-02 2019-02-28 Saudi Basic Industries Corporation Process for upgrading refinery heavy residues to petrochemicals
US11046900B2 (en) * 2013-07-02 2021-06-29 Saudi Basic Industries Corporation Process for upgrading refinery heavy residues to petrochemicals
US11072750B2 (en) * 2013-07-02 2021-07-27 Saudi Basic Industries Corporation Process for upgrading refinery heavy residues to petrochemicals
WO2020128156A1 (en) * 2018-12-17 2020-06-25 Neste Oyj Method to produce high quality components from renewable raw material

Also Published As

Publication number Publication date
DE2360980A1 (de) 1974-07-11
GB1393044A (en) 1975-05-07
FR2212419B3 (enExample) 1976-10-15
BE808149A (fr) 1974-06-04
SE384872B (sv) 1976-05-24
CA1002895A (en) 1977-01-04
JPS4999503A (enExample) 1974-09-20
FR2212419A1 (enExample) 1974-07-26
IT1002359B (it) 1976-05-20
NL7316114A (enExample) 1974-07-02

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