US3556983A - Process for the selective hydrogenation of pyrolysis gasoline - Google Patents

Process for the selective hydrogenation of pyrolysis gasoline Download PDF

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Publication number
US3556983A
US3556983A US767811A US3556983DA US3556983A US 3556983 A US3556983 A US 3556983A US 767811 A US767811 A US 767811A US 3556983D A US3556983D A US 3556983DA US 3556983 A US3556983 A US 3556983A
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United States
Prior art keywords
hydrogenation
catalyst
hydrogen
spinel
temperature
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Expired - Lifetime
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US767811A
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English (en)
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Walter Kronig
Kurt Halcour
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Bayer AG
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Bayer AG
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Priority claimed from DE19671645747 external-priority patent/DE1645747C3/de
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Classifications

    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
    • 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

  • This invention relates to a process for the selective hydrogenation of pyrolysis gasoline.
  • pyrolysis gasoline or fractions thereof can be selectively hydrogenated with good results by hydrogenating pyrolysis gasoline or fractions thereof first at temperatures below 100 C. in the presence of noble metal catalysts on aluminum spinel supports in order selectively to hydrogenate mainly the diolefins, followed by hydrogenating the greater part of the monoolefins in the hydrocarbon mixture thus obtained at temperatures of from 150 to 250 C., using noble metals on aluminum spinel supports as hydrogenation catalysts.
  • the same noble metal catalyst on spinel supports may be used for both hydrogenation stages, below and above 100 C., in the process according to the invention. It has proved advantageous to carry out the hydrogenation above 100 C. immediately after the hydrogenation below 100 C. in the same reactor and at the same pressure.
  • Suitable starting materials include highly unsaturated gasolines, so-called cracked gasolines, obtained in the pyrolysis of liquid hydrocarbons. These cracked gasolines are with advantage subjected to a redistillation before they are used for hydrogenation in order thus to separate off those constituents whose boiling points lie above the boiling range of gasoline.
  • the distillation range is best arranged in such a way that the redistillate has a gum content of less than 5 mg./100 ml. of gasoline.
  • an ageing inhibitor to the distillate, for which purpose the inhibitors used for motor gasoline, preferably the phenolic inhibitors, are suitable, for example di-tert.-butylphenol, in quantities of from about 20 to 100 ppm. Since there is no increase in the gum content where hydrogenation is canied out by the Patented Jan. 19, 1971 process according to the invention, the product of hydrogenation does not have to be subjected to redistillation.
  • the starting materials normally have bromine numbers of from 50 to g/ g and diene contents of from 8 to 25%.
  • fractions thereof for hydrogenation for example certain aromatic fractions such as the BT fraction (benzene-toluene fraction) or the BTX fraction( benzene-toluene-xylene fraction).
  • Noble metals on supports are used as the hydrogenation catalysts.
  • Suitable noble metals include in particular palladium and mixtures of palladium with other noble metals such as platinum, ruthenium, gold and others, and with other additives.
  • Supports containing aluminum spinel are used to support the noble metal. Average pore diameters in the catalyst supports of from 200 to 800 A. and inner surfaces of from 20 to m. /g., have proved to be suitable.
  • the supports containing aluminium spinel may be obtained for example by heating aluminium oxide with spinel-forming compounds. Lithium, beryllium, magnesium, zinc, manganese, cobalt and nickel may be used with particular advantage as the spinel-forming metals. Lithium spinel has proved to be very suitable.
  • the spinel content of the support should amount to at least 20% and preferably to 40% and more. It has proved to be particularly advantageous to use supports of the kind which for the most part, i.e. up to 80-100% for example, consist of spinel in addition optionally to known lubricants or diluents. Among the various other ways of producing spinel-containing supports, it has proved particularly advantageous to start With highly active aluminium oxide in piece form, with an inner surface of from 200* to 350 m. /g.
  • These pieces of aluminium oxide may be impregnated with a solution of a compound (salt, hydroxide) of the spinel-forming metal to be used and then dried.
  • salts are used for impregnation, they are advantageously converted into oxides by heating to 250-650 C., optionally in the presence of gases containing oxygen or steam. This is followed by heating, i.e. calcining, to 900-1300 C., for example for a period of from 1 to 10 hours, in order to perform the spinel formation.
  • the alumina support it is possible repeatedly to impregnate the alumina support with the particular solutions after intermediate drying and decomposition of the salts.
  • One alternative to this is to start with finegrained aluminum oxide With a large inner surface and to add to it a solution of the metal compound, in which case the solution of the metal compound may be added from the outset in such a quantity as corresponds to the subsequent intended level of conversion into spinel.
  • the mass After drying and, optionally, roasting, the mass may be formed in the presence of lubricants for example into strands or pellets and calcined, as described above.
  • the temperatures at which and the periods for which calcination is carried out differ from one type of spinel to the other, although it is readily possible by preliminary tests to determine the conditions to be maintained in order to obtain the required properties in the catalyst support.
  • the calcination temperature and the calcination time affect the inner surface and the pore diameter of the support.
  • the noble metals may be applied to the supports in quantities of for example 0.05 to 5% by weight, advantageously 0.1 to 1% by weight.
  • the support is impregnated for example with an aqueous palladium salt solution and the palladium is deposited on to the support by reduction, for example with formaldehyde in alkaline solution. It is also possible, however, to convert the palladium from inorganic salt form, for example palladium nitrate, or from organic salt form, for example acetate, into the metal by reduction with hydrogen at elevated temperature.
  • the starting material is allowed to trickle in the liquid phase through vertical tubes over the catalyst fixedly arranged in the reaction zone, e.g. as a stationary catalyst bed.
  • Tubes with internal diameters of from 25 to 60 mm., in particular 4060 mm., and lengths of from 3 to 8 meters, may be used to accommodate the catalyst.
  • the temperature is then increased to above 100 C., e.g. about l50250 C., in the second part of the reaction zone. It is possible to control the temperature by surrounding the reaction tubes with heat-transfer agents divided up into two or more chambers, i.e. heating jackets, over the length of the reactor. Water for example may be used as the heat-transfer agent, being cycled through the chambers and an externally situated heat source, for example a heat exchanger. It is possible by virtue of this arrangement to ensure that in the first part of the reactor for example the temperature of the reactants leaving this first part of the hydrogenation remains below 70 C. to 100 C. preferably 95 C., i.e.
  • the hourly throughput of pyrolysis gasoline amounts in the first hydrogenation stage to between 2 and 10, and preferably to between and 7.5 kg./litre of catalyst volume, and in the second stage to between 1 and 5, and preferably to between 2 and 3, kg./litre of catalyst volume.
  • the catalyst volume in the two sections will depend upon the loads prevailing. Between 0.2 and twice the volume of the already hydrogenated or part-hydrogenated product may be recycled from the separators to the head of the reactor(s) and mixed with the feed, for which purpose recycling is preferably carried out without release of pressure.
  • the quantity of hydrogen to be used is generally selected in such a way that it is from 10 to 30% higher than the amount of hydrogen absorbed by chemical bonding into the pyrolysis gasoline.
  • the liquid products may be separated from the gaseous products in a separator arranged behind the reaction zone, whilst gas may be released from the gas zone in such quantities that the required excess of hydrogen is run off here.
  • the extent of which the reaction product is cooled behind the reaction zone is governed by the requirements of stabilisation of the liquid hydrogenated product in a following stabilisation column.
  • the products of hydrogenation have a diene content of less than 1% by weight, usually less than 0.1% by weight.
  • the gum contents before and after ageing are less than 5 mg./ ml., and the induction time for ageing is greater than 240 minutes.
  • the bromine number is usually between 1 and 12 g./ 100 g.
  • the octane numbers of the hydrogenation products with 0.04% by volume of lead tetraethyl (TEL) added thereto are substantially the same as the corresponding octane numbers of the starting materials. Accordingly, it is now possible through this procedure to hydrogenate most of the monoolefins without appreciably affecting the octane rating of the lead-containing gasoline.
  • the procedure described is accompanied by some decomposition of the organic sulphur compounds present in the starting material.
  • the sulphur content of the hydrogenation product leaving the second hydrogenation step is usually between 10 and 80% of the sulphur content of the starting materials. Accordingly, apart from the advantages accompanying removal of the olefins, the starting material is also desulphurized to an appreciable extent, which also contributes towards improving the lead susceptibility of the hydrogenated product 'with respect to the starting material. It is remarkable that, despite this information of hydrogen sulphide, the catalyst retains a satisfactory level of hydrogenation activity. As a result of tests lasting several months, it has been found that the aforementioned catalysts show an extremely constant level of hydrogenation activity.
  • the support was impregnated with a solution of palladium (ID-chloride.
  • the palladium salt was reduced to palladium with alkaline formalin.
  • the catalyst was then washed free of chlorine and dried.
  • the finished catalyst had a palladium content of 0.6% by weight.
  • the catalyst was introduced into a vertically arranged tube 4 metres long with an internal diameter of 24 mm. in a quantity of 1.6 litres. Starting materials and gaseous hydrogen were fed in at the upper end. The two halves of the reactor tube were heated with water separately from one another.
  • Hydrogenation of the pyrolysis gasoline was carried out in a hydrogen atmosphere of 50 atms.
  • the product to be hydrogenated which had been redistilled beforehand, and to which 40 ppm. of di-tert.-butyl phenol had been added as an inhibitor, was introduced with the hydrogen at the upper end of the reactor at 25 C. under a load of 2 kg./ litre hour.
  • the liquid product trickled down over the catalyst in the hydrogen atmosphere.
  • the temperature of the heating water amounted to 75 C., and in the lower half to 220 C., the temperature of the reaction product at the end of the reactor was 220 C.
  • the following table provides a comparison between the properties of two redistilled pyrolysis gasolines from mildand severe-cracking plants with those of the corresponding hydrogenation products obtained therefrom in accordance with the invention.
  • the table also shows the results obtained from hydrogenation in accordance with the invention under the same conditions using a benzene/ toluene fraction of pyrolysis gasoline from short residence time cracking:
  • TEL tetraethyl lead
  • MON Motor octane number
  • Process according to claim 1 for the hydrogenation of pyrolysis gasolines and fractions thereof to reduce the olefin and organic sulfur content thereof which comprises hydrogenating a member selected from the group consisting of pyrolysis gasolines and fractions thereof in a first step at a temperature substantially below between about -95 C. in trickle phase in a substantially static hydrogen atmosphere at a hydrogen pressure substantially between about 20-80 atmospheres in the presence of noble metal on a lithium aluminum spinel as hydrogenation catalyst for the selective hydrogenation substantially of the diolefins contents therein, and thereafter hydrogenating further the hydrocarbon mixture obtained from the first step in a second step at a temperature substantially between about ISO-250 C. in trickle phase in a substantially static hydrogen atmosphere at a hydrogen pressure substantially between about 20-80 atmospheres in the presence of the same catalyst as in the first step for the further selective hydrogenation substantially of the mono-olefins and part of the sulfur content therein.

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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)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US767811A 1967-10-19 1968-10-15 Process for the selective hydrogenation of pyrolysis gasoline Expired - Lifetime US3556983A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19671645747 DE1645747C3 (de) 1967-10-19 1967-10-19 Verfahren zur selektiven Hydrierung von Pyrolysebenzin

Publications (1)

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US3556983A true US3556983A (en) 1971-01-19

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US (1) US3556983A (pl)
ES (1) ES359327A2 (pl)
GB (1) GB1207269A (pl)
PL (1) PL79423B1 (pl)
SE (1) SE347010B (pl)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4456526A (en) * 1982-09-24 1984-06-26 Atlantic Richfield Company Method for minimizing fouling of heat exchangers
US4510041A (en) * 1984-08-10 1985-04-09 Atlantic Richfield Company Method for minimizing fouling of heat exchanger
US4511457A (en) * 1984-08-10 1985-04-16 Atlantic Richfield Company Method for minimizing fouling of heat exchanger
US5057635A (en) * 1990-02-08 1991-10-15 Uop Process for isomerizing olefins in gasoline streams
US5254789A (en) * 1990-02-08 1993-10-19 Uop Process for isomerizing olefins in gasoline streams
US5430221A (en) * 1990-02-08 1995-07-04 Uop Process for isomerizing olefins in gasoline streams
US20100288679A1 (en) * 2007-09-18 2010-11-18 Paul Benjerman Himelfarb Process for the deep desulfurization of heavy pyrolysis gasoline
WO2015000850A1 (en) 2013-07-02 2015-01-08 Saudi Basic Industries Corporation Process and installation for the conversion of crude oil to petrochemicals having an improved btx yield
WO2015128016A1 (en) 2014-02-25 2015-09-03 Saudi Basic Industries Corporation Process for producing btx from a mixed hydrocarbon source using pyrolysis
WO2015128017A1 (en) 2014-02-25 2015-09-03 Saudi Basic Industries Corporation Process for producing btx from a mixed hydrocarbon source using coking
US10358612B2 (en) 2014-02-25 2019-07-23 Saudi Basic Industries Corporation Process for producing BTX from a mixed hydrocarbon source using catalytic cracking

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1055107C (zh) * 1997-11-28 2000-08-02 中国石油化工总公司 一种选择性加氢催化剂

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4456526A (en) * 1982-09-24 1984-06-26 Atlantic Richfield Company Method for minimizing fouling of heat exchangers
US4510041A (en) * 1984-08-10 1985-04-09 Atlantic Richfield Company Method for minimizing fouling of heat exchanger
US4511457A (en) * 1984-08-10 1985-04-16 Atlantic Richfield Company Method for minimizing fouling of heat exchanger
US5057635A (en) * 1990-02-08 1991-10-15 Uop Process for isomerizing olefins in gasoline streams
US5254789A (en) * 1990-02-08 1993-10-19 Uop Process for isomerizing olefins in gasoline streams
US5430221A (en) * 1990-02-08 1995-07-04 Uop Process for isomerizing olefins in gasoline streams
CN101802139B (zh) * 2007-09-18 2013-10-30 国际壳牌研究有限公司 重热解汽油的深度脱硫方法
US8163167B2 (en) 2007-09-18 2012-04-24 Shell Oil Company Process for the deep desulfurization of heavy pyrolysis gasoline
US20100288679A1 (en) * 2007-09-18 2010-11-18 Paul Benjerman Himelfarb Process for the deep desulfurization of heavy pyrolysis gasoline
EP3395929A1 (en) 2007-09-18 2018-10-31 Shell Internationale Research Maatschappij B.V. Process for the deep desulfurization of heavy pyrolysis gasoline
WO2015000850A1 (en) 2013-07-02 2015-01-08 Saudi Basic Industries Corporation Process and installation for the conversion of crude oil to petrochemicals having an improved btx yield
US9862898B2 (en) 2013-07-02 2018-01-09 Saudi Basic Industries Corporation Process and installation for the conversion of crude oil to petrochemicals having an improved BTX yield
WO2015128016A1 (en) 2014-02-25 2015-09-03 Saudi Basic Industries Corporation Process for producing btx from a mixed hydrocarbon source using pyrolysis
WO2015128017A1 (en) 2014-02-25 2015-09-03 Saudi Basic Industries Corporation Process for producing btx from a mixed hydrocarbon source using coking
US10131854B2 (en) 2014-02-25 2018-11-20 Saudi Basic Industries Corporation Process for producing BTX from a mixed hydrocarbon source using coking
US10131853B2 (en) 2014-02-25 2018-11-20 Saudi Basic Industries Corporation Process for producing BTX from a mixed hydrocarbon source using pyrolysis
US10358612B2 (en) 2014-02-25 2019-07-23 Saudi Basic Industries Corporation Process for producing BTX from a mixed hydrocarbon source using catalytic cracking
US10563136B2 (en) 2014-02-25 2020-02-18 Saudi Basic Industries Corporation Process for producing BTX from a mixed hydrocarbon source using pyrolysis

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Publication number Publication date
GB1207269A (en) 1970-09-30
PL79423B1 (pl) 1975-06-30
SE347010B (pl) 1972-07-24
ES359327A2 (es) 1970-06-01

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