WO1999015485A1 - Hydrogenation selective - Google Patents

Hydrogenation selective Download PDF

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Publication number
WO1999015485A1
WO1999015485A1 PCT/GB1998/002590 GB9802590W WO9915485A1 WO 1999015485 A1 WO1999015485 A1 WO 1999015485A1 GB 9802590 W GB9802590 W GB 9802590W WO 9915485 A1 WO9915485 A1 WO 9915485A1
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WO
WIPO (PCT)
Prior art keywords
volume
acetylene
ppm
bed
hydrogenation
Prior art date
Application number
PCT/GB1998/002590
Other languages
English (en)
Inventor
Bernard John Crewdson
Stephen Bailey
Original Assignee
Imperial Chemical Industries Plc
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 Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to AU88746/98A priority Critical patent/AU8874698A/en
Publication of WO1999015485A1 publication Critical patent/WO1999015485A1/fr

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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
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/02—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to selective hydrogenation and in particular to the catalytic selective hydrogenation of acetylenes in the presence of olefins, especially ethylene
  • Olefins such as ethylene are generally made by thermal cracking a hydrocarbon feedstock containing saturated hydrocarbons containing two or more carbon atoms Typically the feedstock is ethane, LPG, or a naphtha cut from a refinery
  • the product from the cracker herein termed cracked gas, generally contains a variety of materials including hydrogen, methane, saturated and unsaturated C 2 hydrocarbons, saturated and unsaturated C 3 hydrocarbons, and saturated and unsaturated higher hydrocarbons
  • the cracked gas generally contains small proportions of acetylene and other compounds that are more highly unsaturated than mono-olefins It is normally desirable to remove the acetylene and such more highly unsaturated compounds The removal of acetylene and other highly unsaturated components is normally effected by selective hydrogenation
  • the cracked gas will generally also contain steam, carbon oxides, and sulphur compounds Normally the cracked gas is cooled and then compressed, e g to a pressure in the range 10-40 bar abs, and then subjected to fractional distillation to effect separation Usually hydrogen sulphide and carbon dioxide are separated from the cracked gas, e g by means of a caustic wash, prior to the fractional distillation
  • tail-end selective hydrogenation In some cases, hydrogen and methane are first separated from the cracked gas, before or a ter such a washing step Subsequent acetylene removal by selective hydrogenation is termed “tail-end” selective hydrogenation and is normally effected after fractional distillation Since the hydrogen in the cracked gas has been removed, it is necessary in “tail-end” selective hydrogenation to re-introduce hydrogen The amount of hydrogen added is normally limited so that there is not a large excess over that required to hydrogenate the acetylene and any other components that are more highly unsaturated than mono-olefins that may be present in the stream being selectively hydrogenated Normally the hydrogen content of the gas subjected to selective hydrogenation in a tail-end process is less than about 5% by volume, usually less than 3% by volume
  • the selective hydrogenation is effected on a gas stream containing the hydrogen and methane, possibly after some separation step to remove high boiling components, e g C 5 and higher hydrocarbons
  • the selective hydrogenation process is termed "front-end” selective hydrogenation and is thus effected on a gas stream containing a relatively large proportion of hydrogen, much larger than is required to effect hydrogenation of the acetylene and any other components that are more highly unsaturated than mono-olefins remaining in the gas stream
  • the selective hydrogenation may be effected on the "total cracked gas", generally after separation of C 5 hydrocarbons and higher boiling components, or on a "light” stream produced by distillation: the distillation stage is usually either "de-ethanisation” wherein a light stream containing C 2 hydrocarbons and lighter materials is separated from a heavy stream containing C 3 and higher hydrocarbons, or "de-propanisation” wherein a light stream containing C
  • the light stream contains hydrogen, carbon monoxide, methane, ethane, ethylene and acetylene.
  • the fractional distillation is de-propanisation
  • the light stream will also contain propane, propylene, methyl acetylene, and propadiene.
  • the light stream may also contain small amounts of butadiene.
  • the gas stream in a front-end selective hydrogenation process will contain more than 10% by volume of hydrogen but a total of less than 2% by volume of acetylene and other components more highly unsaturated than mono-olefins.
  • the concentration of acetylene in the light stream is typically 2000 to 10000 ppm by volume.
  • the concentrations of methyl acetylene, propadiene and butadiene are generally each less than 5000 ppm by volume.
  • the selective hydrogenation is normally effected by passing the light stream, in some cases after passage through guard beds to remove contaminants such as arsenic and mercury compounds, at an inlet temperature in the range 60 to 90°C, through a fixed bed of a particulate selective hydrogenation catalyst, typically in the form of a support, e.g. alumina, impregnated with palladium and sometimes also silver or copper.
  • a particulate selective hydrogenation catalyst typically in the form of a support, e.g. alumina, impregnated with palladium and sometimes also silver or copper.
  • the selective hydrogenation may be effected in a single stage using a reactor provided with cooling means, so that the process approximates to isothermal operation, normally it is effected in two or more stages using adiabatic beds of catalyst, with cooling between stages.
  • the reason for such multistage operation with inter-stage cooling is that the hydrogenation processes are exothermic leading to a significant temperature increase: a series of beds with inter-bed cooling, rather than a single bed, is normally used to keep the temperature to a minimum since as the temperature increases, the hydrogenation becomes less selective and an increasing amount of the olefins are also hydrogenated.
  • the present invention provides a process for the selective hydrogenation of a feed gas stream containing at least 10% by volume of hydrogen, ethylene and a total of 4000 to 15000 ppm by volume of hydrocarbons containing 2 to 4 carbon atoms that are more highly unsaturated than mono-olefins, and including 2000 to 10000 ppm by volume of acetylene and not more than 5000 ppm by volume of each of methyl acetylene, propadiene and butadiene, by passing the gas stream adiabatically through a fixed bed of a particulate selective hydrogenation catalyst at an inlet temperature in the range 60 to 90°C, characterised in that the inlet temperature and flow rate to the bed are such that at least 80% by volume, and not less than 4000 ppm by volume, of said more highly unsaturated compounds are hydrogenated in said bed, the outlet temperature is below the runaway temperature of the catalyst, and the difference between the outlet and inlet temperatures of said bed is not more than 80% of the difference between the clean-up and run
  • the "clean-up" and “runaway” temperatures for the catalyst are determined by the following procedure. 20 ml of the catalyst is placed in a stainless steel reactor tube of about 12 mm internal diameter and about 46 cm length and reduced under flowing hydrogen at a pressure of about 14 bar g. at a temperature of about 50°C for about 16 hours. The reactor is then cooled to about 43°C and then a test gas containing 26.6% methane, 14.1 % ethane, 39.2% ethylene, 2680 ppm acetylene, 210 ppm carbon monoxide, balance, i.e. almost 20%, hydrogen (% and ppm by volume) is introduced at 900 ml/minute. The reactor temperature is then increased gradually and samples of the exit gas are analysed.
  • the "clean-up" temperature is that temperature at which the acetylene content of the product was 10 ppm by volume
  • the "runaway” temperature is that temperature where the ethylene to ethane molar ratio of the product was 2.3 indicating that about 5% of the ethylene had been hydrogenated.
  • the difference between the "clean-up” and “runaway” temperatures is at least 40°C.
  • Preferred catalysts are catalysts E6, F3 to F12, F15 to F19, G2, G3, G5 to G7 and I of the aforementioned US 5488 024.
  • Other suitable catalysts include supported palladium/silver catalysts also containing alkali metal compounds, e.g. fluorides, possibly with additional fluorine compounds, as described in US 5 583 274 and US 5 587 348.
  • the process is operated such that there is an increase in the olefin molar content of the gas amounting to at least half of the molar amount of acetylene, methyl acetylene, propadiene and butadiene hydrogenated.
  • the bulk, i.e. at least 80% by volume, of the more highly unsaturated hydrocarbons are hydrogenated during passage through the catalyst bed, subject to hydrogenation of at least 4000 ppm of the more highly unsaturated hydrocarbons.
  • the desired hydrogenation can be achieved in a single bed, but in some cases, where the feed contains a high proportion of the more highly unsaturated hydrocarbons, e.g.
  • the inlet temperature employed is preferably the minimum consistent with achieving the desired acetylene content of the product gas.
  • the reaction is preferably operated at a pressure in the range 10 to 40 bar abs. and at a space velocity (at NTP) of 3000 to 8000 h 1 .
  • the process is preferably operated on such a scale that the volume of catalyst employed is at least 0.5 m 3 , particularly at least 1 m 3 .
  • the process is controlled by control of the inlet temperature to the bed.
  • the process is preferably applied to the hydrogenation of total cracked gas or to light olefin-containing streams produced as aforesaid by subjecting cracked gas to de-ethanisation or de-propanisation.
  • the process may however also be applied to other olefin-containing streams containing more than 10% by volume of hydrogen.
  • Example 1 A catalyst A containing 0.02% by weight of palladium and 0.07% by weight of zinc supported on alumina was prepared by impregnating alpha-alumina spheres of 4-5 mm diameter and having a narrow, unimodal, pore size distribution and surface area no greater than 4 m 2 /g with a mixed aqueous solution of palladium and zinc nitrates. After impregnation, the spheres were calcined in air at 450°C for 4 hours. The "clean-up” and “runaway” temperatures were 53°C and 80°C respectively and so this catalyst could be used in processes where the temperature rise through hydrogenation was less than about 22°C.
  • Example 2 A catalyst B also containing 0.02% by weight of palladium and 0.07% by weight of zinc supported on alumina was prepared in the same was as Catalyst A except that the alpha-alumina was in the form of pellets of 5 mm diameter and 3 mm height which again have a narrow, unimodal pore size distribution and surface area less than 4 m 2 /g, and the pellets were immersed in aqueous sodium hydroxide solution followed by drying at 150°C before impregnation with the palladium and zinc nitrates solution.
  • the "clean-up” and “runaway” temperatures were 63°C and about 103°C respectively and so this catalyst could be used in processes where the temperature rise through hydrogenation was less than about 32°C.
  • Example 3 Similarly computer modelling shows that a catalyst such as Catalyst F18 described in the aforesaid US 5 488 024 having "clean-up” and “runaway” temperatures of about 72°C and about 146°C respectively could be employed for the adiabatic selective hydrogenation of a feed gas containing 20 mol% methane, 35 mol% ethylene, 5 mol% ethane, 0.6 mol% acetylene, 0.4 mol% methyl acetylene, 0.02 mol% carbon monoxide and balance, about 39%, hydrogen at an inlet temperature of 75°C to give a product having an acetylene content below 1 ppm by volume and a methyl acetylene content below 500 ppm by volume at an outlet temperature of 115°C, representing a temperature rise of 40°C.
  • the amount of ethylene hydrogenated is less than the amount produced through hydrogenation of the acetylene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une hydrogénation sélective d'un filet gazeux d'alimentation contenant au moins 10 % en volume d'hydrogène, d'éthylène et un total compris entre 4.000 et 15.000 ppm en volume d'hydrocarbures renfermant entre 2 et 4 atomes de carbone qui sont plus fortement insaturés que les mono-oléfines et renfermant entre 2.000 et 10.000 ppm en volume d'acétylène et ne dépassant pas 5.000 ppm en volume de chaque méthylacétylène, propadiène et butadiène. Pour effectuer ladite hydrogénation, il faut passer le filet gazeux adiabatiquement à travers un lit d'un catalyseur d'hydrogénation sélective à une température d'entrée comprise entre 60 et 90 °C. La température d'entrée et la vitesse d'écoulement vers le lit sont telles qu'au moins 80 % en volume et au moins 4.000 ppm en volume desdits composés plus fortement insaturés sont hydrogénés dans ledit lit. La température de sortie est inférieure à la température aberrante du catalyseur et la différence entre les températures de sortie et d'entrée desdits lits ne dépasse pas 80 % de la différence entre les températures de désencrassage et aberrante dudit catalyseur.
PCT/GB1998/002590 1997-09-25 1998-08-27 Hydrogenation selective WO1999015485A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU88746/98A AU8874698A (en) 1997-09-25 1998-08-27 Selective hydrogenation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9720333.5 1997-09-25
GBGB9720333.5A GB9720333D0 (en) 1997-09-25 1997-09-25 Selective hydrogenation

Publications (1)

Publication Number Publication Date
WO1999015485A1 true WO1999015485A1 (fr) 1999-04-01

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ID=10819585

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/002590 WO1999015485A1 (fr) 1997-09-25 1998-08-27 Hydrogenation selective

Country Status (3)

Country Link
AU (1) AU8874698A (fr)
GB (1) GB9720333D0 (fr)
WO (1) WO1999015485A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005097948A2 (fr) * 2004-03-31 2005-10-20 Eastman Chemical Company Procedes et dispositifs pour l'elimination d'acetylene

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995015365A1 (fr) * 1993-12-01 1995-06-08 Imperial Chemical Industries Plc Hydrogenation selective a lits multiples d'acetylenes
US5488024A (en) * 1994-07-01 1996-01-30 Phillips Petroleum Company Selective acetylene hydrogenation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995015365A1 (fr) * 1993-12-01 1995-06-08 Imperial Chemical Industries Plc Hydrogenation selective a lits multiples d'acetylenes
US5488024A (en) * 1994-07-01 1996-01-30 Phillips Petroleum Company Selective acetylene hydrogenation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005097948A2 (fr) * 2004-03-31 2005-10-20 Eastman Chemical Company Procedes et dispositifs pour l'elimination d'acetylene
WO2005097948A3 (fr) * 2004-03-31 2006-01-12 Eastman Chem Co Procedes et dispositifs pour l'elimination d'acetylene
US7525000B2 (en) 2004-03-31 2009-04-28 Eastman Chemical Company Acetylene removal methods and apparatus

Also Published As

Publication number Publication date
AU8874698A (en) 1999-04-12
GB9720333D0 (en) 1997-11-26

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