EP2950928A1 - Procédé de déshydrogénation oxydative de n-butènes en butadiène - Google Patents

Procédé de déshydrogénation oxydative de n-butènes en butadiène

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Publication number
EP2950928A1
EP2950928A1 EP13798701.2A EP13798701A EP2950928A1 EP 2950928 A1 EP2950928 A1 EP 2950928A1 EP 13798701 A EP13798701 A EP 13798701A EP 2950928 A1 EP2950928 A1 EP 2950928A1
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EP
European Patent Office
Prior art keywords
catalyst
oxygen
temperature
volume
gas
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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.)
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EP13798701.2A
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German (de)
English (en)
Inventor
Philipp GRÜNE
Wolfgang RÜTTINGER
Christian Walsdorff
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BASF SE
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BASF SE
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Priority to EP13798701.2A priority Critical patent/EP2950928A1/fr
Publication of EP2950928A1 publication Critical patent/EP2950928A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8878—Chromium
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/18—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a process for the oxidative dehydrogenation of n-butenes to butadiene.
  • Butadiene is an important basic chemical and is used for example for the production of synthetic rubbers (butadiene homopolymers, styrene-butadiene rubber or nitrile rubber) or for the production of thermoplastic terpolymers (acrylonitrile-butadiene-styrene copolymers).
  • Butadiene is further converted to sulfolane, chloroprene and 1, 4-hexamethylenediamine (over 1, 4-dichlorobutene and adiponitrile).
  • dimerization of butadiene vinylcyclohexene can also be produced, which can be dehydrogenated to styrene.
  • Butadiene can be prepared by thermal cracking (steam cracking) of saturated hydrocarbons, usually starting from naphtha as the raw material. Steam cracking of naphtha produces a hydrocarbon mixture of methane, ethane, ethene, acetylene, propane, propene, propyne, allenes, butanes, butenes, butadiene, butynes, methylalls, Cs and higher hydrocarbons.
  • Butadiene can also be obtained by oxidative dehydrogenation of n-butenes (1-butene and / or 2-butene).
  • n-butenes 1,3-butene and / or 2-butene
  • any n-butenes containing mixture can be used.
  • a fraction containing n-butenes (1-butene and / or 2-butene) as a main component and obtained from the C 4 fraction of a naphtha cracker by separating butadiene and isobutene can be used.
  • gas mixtures which comprise 1-butene, cis-2-butene, trans-2-butene or mixtures thereof and which have been obtained by dimerization of ethylene can also be used as starting gas.
  • n-butenes containing gas mixtures obtained by catalytic fluid cracking (FCC) can be used as the starting gas.
  • Gas mixtures containing n-butenes, which are used as the starting gas in the oxidative dehydrogenation of n-butenes to butadiene can also be prepared by non-oxidative dehydrogenation of n-butane-containing gas mixtures.
  • WO2009 / 124945 discloses a shell catalyst for the oxidative dehydrogenation of 1-butene and / or 2-butene to butadiene, which is obtainable from a catalyst precursor comprising
  • X 2 Si and / or Al
  • X 3 Li, Na, K, Cs and / or Rb,
  • y a number determined by the valency and frequency of elements other than oxygen, assuming charge neutrality
  • WO 2010/137595 discloses a multimetal oxide catalyst for the oxidative dehydrogenation of alkenes to dienes which comprises at least molybdenum, bismuth and cobalt, of the general formula MoaBibCOcNidFe e XfYgZhSiiOj
  • X is at least one member selected from the group consisting of magnesium (Mg), calcium (Ca), zinc (Zn), cerium (Ce) and samarium (Sm).
  • Y is at least one element from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and thallium (Tl).
  • Z is at least one element selected from the group consisting of boron (B), phosphorus (P), arsenic (As) and tungsten (W).
  • a catalyst of the composition
  • coke precursors can be formed, such as styrene, anthraquinone and fluorenone, which can eventually lead to coking and deactivation of the multimetal oxide catalyst.
  • the formation of carbonaceous deposits can increase the pressure drop over the catalyst bed. It is possible, for regeneration, to burn off the carbon deposited on the multimetal oxide catalyst at regular intervals with an oxygen-containing gas to restore the activity of the catalyst.
  • JP 60-058928 describes the regeneration of a multimetal oxide catalyst for the oxidative dehydrogenation of n-butenes to butadiene, containing at least molybdenum, bismuth, iron, cobalt and antimony, with an oxygen-containing gas mixture at a temperature of 300 to 700 ° C, preferably 350 to 650 ° C, and an oxygen concentration of 0.1 to 5 vol .-%.
  • oxygen-containing gas mixture air is supplied, which is diluted with suitable inert gases such as nitrogen, water vapor or carbon dioxide.
  • WO 2005/047226 describes the regeneration of a multimetal oxide catalyst for the partial oxidation of acrolein to acrylic acid containing at least molybdenum and vanadium by passing an oxygen-containing gas mixture at a temperature of from 200 to 450.degree.
  • oxygen-containing gas mixture lean air is preferably used with 3 to 10 vol .-% oxygen.
  • the gas mixture may contain water vapor.
  • the object of the invention is to provide a process for the oxidative dehydrogenation of n-butenes to butadiene, in which the regeneration of the multimetal oxide catalyst is as simple as possible.
  • the object is achieved by a process for the oxidative dehydrogenation of n-butenes to butadiene, comprising two or more production steps (i) and at least one regeneration step (ii), in which
  • Catalyst containing at least molybdenum and another metal is brought into contact, and, before the relative loss of conversion at constant temperature> 25%, (ii) in a regeneration step, the multimetal oxide catalyst by passing an oxygen-containing regeneration gas mixture at a temperature of 200 to 450 ° C over the fixed catalyst bed and burning the carbon deposited on the catalyst is regenerated, wherein the regeneration step (ii) between two production steps (i) is carried out, characterized in that per regeneration step (ii) 5 to 50 wt .-% of The catalyst deposited carbon is burned off.
  • per regeneration step (ii) 5 to 50 wt .-% of The catalyst deposited carbon is burned off.
  • the activity of the multimetal oxide catalyst is generally restored by more than 95%, preferably by more than 98%, and in particular by more than 99%, based on the activity of the multimetal oxide catalyst at the beginning of the preceding production step (i).
  • a regeneration step (ii) is carried out when the relative loss of sales (that is, based on the conversion at the beginning of the respective production step (i)) at constant temperature is at most 25%.
  • a regeneration step (ii) is carried out before the relative loss of conversion at constant temperature is greater than 15%, more preferably before the loss of conversion is greater than 10%.
  • a regeneration step (ii) is performed only when the constant-temperature relative loss of conversion is at least 2%.
  • a production step (i) has a duration of 5 to 5000 hours until a relative loss of sales of up to 25%, based on the conversion at the beginning of this production step (i), is reached.
  • the catalyst can go through up to 5000 or more cycles of production and regeneration steps.
  • the amount of carbon deposited and spent on the catalyst can be determined by quantitative measurement of the carbon oxides formed during the respective regeneration step (ii), for example by online IR determination of the carbon oxides in the exhaust gases of the regeneration.
  • the amount of carbon deposited as a whole on the catalyst is determined by total combustion of the carbon at at least 400 ° C. with a mixture of 10% by volume of oxygen, 80% by volume of nitrogen and 10% by volume of steam. The temperature is chosen so that no further formation of carbon oxides takes place with a further increase in the temperature.
  • the amount of carbon deposits on the catalyst can be made by measuring the carbon content of samples taken from the catalyst.
  • Catalysts suitable for oxydehydrogenation are generally based on a Mo-Bi-O-containing multimetal oxide system, which generally additionally contains iron.
  • the catalyst system contains further additional components from FIG. 1. to 15th group of the periodic table, such as potassium, cesium, magnesium, zirconium, chromium, nickel, cobalt, cadmium, tin, lead, germanium, lanthanum, manganese, tungsten, phosphorus, cerium, aluminum or silicon.
  • Iron-containing ferrites have also been proposed as catalysts.
  • the multimetal oxide contains cobalt and / or nickel.
  • the multimetal oxide contains chromium.
  • the multimetal oxide contains manganese.
  • the catalytically active molybdenum and at least one further metal-containing multimetal oxide has the general formula (I):
  • X 1 W, Sn, Mn, La, Ce, Ge, Ti, Zr, Hf, Nb, P, Si, Sb, Al, Cd and / or Mg;
  • X 2 Li, Na, K, Cs and / or Rb,
  • a 0.1 to 7, preferably 0.3 to 1.5;
  • b 0 to 5, preferably 2 to 4;
  • c 0 to 10, preferably 3 to 10;
  • e 0 to 5, preferably 0.1 to 2;
  • f 0 to 24, preferably 0.1 to 2;
  • g 0 to 2, preferably 0.01 to 1;
  • the catalyst may be a bulk material catalyst or a shell catalyst. If it is a shell catalyst, it has a carrier body (a) and a shell (b) containing the catalytically active, molybdenum and at least one further metal-containing multimetal.
  • Support materials suitable for shell catalysts are e.g. porous or preferably non-porous aluminum oxides, silicon dioxide, zirconium dioxide, silicon carbide or silicates such as magnesium or aluminum silicate (for example C 220 steatite from CeramTec).
  • the materials of the carrier bodies are chemically inert.
  • the support materials may be porous or non-porous.
  • the carrier material is preferably non-porous (total volume of the pores based on the volume of the carrier body preferably ⁇ 1% by volume).
  • substantially non-porous, surface roughness, spherical supports made of steatite eg steatite type C 220 from. CeramTec
  • the diameter of 1 to 8 mm preferably 2 to 6 mm, particularly preferably 2 to 3 or 4 to 5 mm.
  • cylinders made of carrier material as the support body whose length is 2 to 10 mm and whose outer diameter is 4 to 10 mm.
  • the wall thickness is usually 1 to 4 mm.
  • annular carrier body Preferably to be used annular carrier body have a length of 2 to 6 mm, a NEN outside diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm.
  • the layer thickness of shell (b) of a molybdenum and at least one further metal-containing multimetal oxide composition is generally from 5 to 1000 ⁇ m. Preferably 10 to 800 ⁇ , more preferably 50 to 600 ⁇ and most preferably 80 to 500 ⁇ .
  • Mo-Bi-Fe-O-containing multimetal oxides are Mo-Bi-Fe-Cr-O or Mo-Bi-Fe-Zr-O-containing multimetal oxides.
  • Preferred systems are described, for example, in US 4,547,615 (Moi2BiFeo, iNi 8 ZrCr 3 Ko, 20x and Moi2BiFeo, iNi 8 AICr 3 Ko, 20x), US 4,424,141
  • Particularly preferred catalytically active, molybdenum and at least one further metal-containing multimetal oxides have the general formula (Ia):
  • X 1 Si, Mn and / or Al
  • X 2 Li, Na, K, Cs and / or Rb,
  • y a number determined on the assumption of charge neutrality by the valence and frequency of the elements other than oxygen in (1a).
  • the stoichiometric coefficient a in formula (Ia) is preferably 0.4 ⁇ a 1, more preferably 0.4 ⁇ 0.95.
  • the value for the variable b is preferably in the range 1 ⁇ b ⁇ 5 and particularly preferably in the range 2 ⁇ b ⁇ 4.
  • the sum of the stoichiometric coefficients c + d is preferably in the range 4 ⁇ c + d 8, and particularly preferably in Range 6 S c + ds 8.
  • the stoichiometric coefficient e is preferably in the range 0.1 S es 2, and particularly preferably in the range 0.2 ⁇ e ⁇ 1.
  • the stoichiometric coefficient g is expediently> 0. Preference is given to 0.01 ⁇ g ⁇ 0.5 and more preferably 0.05 to 0.2 g.
  • the coated catalyst is prepared by applying to the carrier body by means of a binder a layer containing the molybdenum and at least one further metal-containing multimetal oxide, drying and calcining the coated carrier body.
  • finely divided, molybdenum-containing and at least one further metal-containing multimetal oxides are basically obtainable by forming an intimate dry mixture of starting compounds of the elemental constituents of the catalytically active oxide composition and thermally treating the intimate dry mixture at a temperature of from 150 to 650 ° C.
  • suitable finely divided multimetal oxide compositions starting from known starting compounds of the elemental constituents of the desired multimetal oxide composition in the respective stoichiometric ratio is started, and from these produces a very intimate, preferably finely divided dry mixture, which is then subjected to the thermal treatment.
  • the sources can either already be oxides, or those compounds which can be converted into oxides by heating, at least in the presence of oxygen.
  • suitable starting compounds are, in particular, halides, nitrates, formates, oxalates, acetates, carbonates or hydroxides.
  • Suitable starting compounds of molybdenum are also its oxo compounds (molybdate) or the acids derived therefrom.
  • Suitable starting compounds of Bi, Cr, Fe and Co are in particular their nitrates.
  • the intimate mixing of the starting compounds can in principle be carried out in dry form or in the form of aqueous solutions or suspensions.
  • an aqueous suspension may be prepared by combining a solution containing at least molybdenum and an aqueous solution containing the remaining metals. Alkali metals or alkaline earth metals can be present in both solutions.
  • a precipitation is carried out, which leads to the formation of a suspension.
  • the temperature of the precipitation may be higher than room temperature, preferably from 30 ° C to 95 ° C, and more preferably from 35 ° C to 80 ° C.
  • the suspension may then be aged at elevated temperature for a period of time.
  • the aging period is generally between 0 and 24 hours, preferably between 0 and 12 hours, and more preferably between 0 and 8 hours.
  • the temperature of aging is generally between 20 ° C and 99 ° C, preferably between 30 ° C and 90 ° C, and more preferably between
  • the pH of the mixed solutions or suspension is generally between pH 1 and pH 12, preferably between pH 2 and pH 11 and more preferably between pH 3 and pH 10.
  • the drying step may be generally carried out by evaporation, spray drying or freeze drying or the like.
  • the drying is carried out by spray drying.
  • the suspension is sprayed at elevated temperature with a spray head whose temperature is generally 120 ° C. to 300 ° C., and the dried product is collected at a temperature of> 60 ° C.
  • the residual moisture, determined by drying the spray powder at 120 ° C, is generally less than 20 wt .-%, preferably less than 15 wt .-% and particularly preferably less than 12 wt .-%.
  • the spray powder is transferred in a further step in a shaped body.
  • shaping aids e.g. Water, boron trifluoride or graphite into consideration.
  • lubricants e.g. Water, boron trifluoride or graphite into consideration.
  • Based on the mass to be molded into the catalyst precursor body in general ⁇ 10% by weight, usually ⁇ 6% by weight, often ⁇ 4% by weight of shaping assistant is added. Usually, the aforementioned additional amount is> 0.5 wt .-%.
  • Preferred lubricant is graphite.
  • the thermal treatment of the Katalysatorvor Wunsch Moments is usually carried out at temperatures exceeding 350 ° C. Normally, the temperature of 650 ° C is not exceeded during the thermal treatment.
  • the temperature of 600 ° C. preferably the temperature of 550 ° C. and particularly preferably the temperature of 500 ° C.
  • the thermal treatment of the catalyst precursor molded body preferably the temperature of 380 ° C, advantageously the temperature of 400 ° C, with particular advantage the temperature of 420 ° C and most preferably the temperature of 440 ° C exceeded.
  • the thermal treatment can also be divided into several sections in their time sequence.
  • the thermal treatment of the catalyst precursor body takes several hours (usually more than 5 h) to complete. Often, the total duration of the thermal treatment extends to more than 10 hours. Treatment times of 45 hours and 35 hours are usually not exceeded within the scope of the thermal treatment of the catalyst precursor molding. Often the total treatment time is less than 30 h.
  • 500 ° C are not exceeded in the thermal treatment of the Katalysatorfor headphonesrform stresses and the treatment time in the temperature window of> 400 ° C extends to 5 to 30 h.
  • the thermal treatment (calcination) of the catalyst precursor moldings can be carried out both under inert gas and under an oxidative atmosphere such as e.g. Air as well as under a reducing atmosphere (for example in mixtures of inert gas, NH 3, CO and / or H 2 or methane). Of course, the thermal treatment can also be carried out in a vacuum. In principle, the thermal treatment of the catalyst precursor moldings in a variety of furnace types such. heated convection chambers, Horde ovens, rotary kilns, belt calciners or shaft furnaces are performed. The thermal treatment of the catalyst precursor shaped bodies preferably takes place in a belt calcination device, as recommended by DE-A 10046957 and WO 02/24620.
  • the thermal treatment of the catalyst precursor moldings below 350 ° C usually pursues the thermal decomposition of the sources of elemental constituents of the desired catalyst contained in the catalyst precursor moldings. Often, in the process according to the invention, this decomposition phase takes place during the heating to temperatures ⁇ 350.degree.
  • the catalytically active metal oxide composition obtained after the calcination can then be converted by grinding into a finely divided powder for the preparation of a coated catalyst, which is then applied with the aid of a liquid binder to the outer surface of a carrier body.
  • the fineness of the catalytically active oxide mass applied to the surface of the carrier body is adapted to the desired shell thickness.
  • Suitable carrier materials for the preparation of coated catalysts are porous or preferably non-porous aluminum oxides, silicon dioxide, zirconium dioxide, silicon carbide or silicates such as magnesium or aluminum silicate (for example C 220 steatite from CeramTec).
  • the materials of the carrier bodies are chemically inert.
  • the support materials may be porous or non-porous.
  • the support material is not porous (total volume of the pores, based on the volume of the support body, preferably -i 1 vol .-%).
  • Preferred hollow cylinders as support bodies have a length of 2 to 10 mm and an outer diameter of 4 to 10 mm.
  • the wall thickness is moreover preferably 1 to 4 mm.
  • Particularly preferred annular carrier bodies have a length of 2 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm.
  • An example are rings of geometry 7 mm x 3 mm x 4 mm (outer diameter x length x inner diameter) as a carrier body.
  • the layer thickness D of a molybdenum and at least one further metal containing Muletetalloxidmasse is usually from 5 to 1000 ⁇ .
  • Preferred are 10 to 800 ⁇ , more preferably 50 to 600 ⁇ and most preferably 80 to 500 ⁇ .
  • the application of the molybdenum and at least one further metal-containing multimetal oxide to the surface of the carrier body can be carried out according to the methods described in the prior art, for example as described in US-A 2006/0205978 and EP-A 0 714 700.
  • the finely divided metal oxide materials are applied to the surface of the carrier body or to the surface of the first layer with the aid of a liquid binder.
  • a liquid binder e.g. Water, an organic solvent or a solution of an organic substance (e.g., an organic solvent) in water or in an organic solvent.
  • the liquid binder used is particularly advantageously a solution consisting of 20 to 95% by weight of water and 5 to 80% by weight of an organic compound.
  • the organic fraction of the abovementioned liquid binders is preferably from 10 to 50% by weight and more preferably from 10 to 30% by weight.
  • organic binders or binder constituents whose boiling point or sublimation temperature at normal pressure (1 atm) is> 100 ° C., preferably> 150 ° C.
  • the boiling point or sublimation point of such organic binders or binder constituents at atmospheric pressure is at the same time below the highest calcination temperature used in the preparation of the molybdenum-containing finely divided multimetal oxide.
  • this highest calcination temperature is ⁇ 600 ° C, often ⁇ 500 ° C. Examples which may be mentioned as organic binders mono- or polyhydric organic alcohols such.
  • organic binder promoters soluble in water in an organic liquid or in a mixture of water and an organic liquid, e.g. Monosaccharides and oligosaccharides such as glucose, fructose, sucrose and / or lactose suitable.
  • liquid binders are solutions which consist of 20 to 95% by weight of water and 5 to 80% by weight of glycerol.
  • the glycerol content in these aqueous solutions is from 5 to 50% by weight and more preferably from 8 to 35% by weight.
  • the application of the molybdenum-containing finely divided multimetal oxide can be carried out in such a way that the finely divided mass of molybdenum-containing multimetal oxide in the liquid dispersed binder and sprayed the resulting suspension on moving and possibly hot carrier body, as described in DE-A 1642921, DE-A 2106796 and DE-A 2626887. After completion of spraying, as described in DE-A 2909670, By passing hot air, the moisture content of the resulting shell catalysts can be reduced.
  • pore formers such as malonic acid, melamine, nonylphenol ethoxylate, stearic acid, glucose, starch, fumaric acid and succinic acid can be added to produce a suitable pore structure of the catalyst and to improve the mass transfer properties.
  • the catalyst preferably contains no pore formers.
  • the carrier body is first moistened with the liquid binder, and subsequently the finely divided mass of multimetal oxide is applied to the surface of the carrier body moistened with the binder by rolling the moistened carrier body in the finely divided mass.
  • the process described above is preferably repeated several times, d. H. the base-coated carrier body is moistened again and then coated by contact with dry finely divided mass.
  • the support bodies to be coated are filled into a preferably tilted rotary container (for example a turntable or coating pan) which rotates (the angle of inclination is generally 30 to 90 °).
  • the temperatures necessary to effect the removal of the coupling agent are below the highest calcination temperature of the catalyst, generally between 200 ° C and 600 ° C.
  • the catalyst is heated to 240 ° C to 500 ° C, and more preferably to temperatures between 260 ° C and 400 ° C.
  • Primer may take several hours.
  • the catalyst is generally heated at said temperature for between 0.5 and 24 hours to remove the coupling agent.
  • the time is between 1.5 and 8 hours, and more preferably between 2 and 6 hours.
  • a flow around the catalyst with a gas can accelerate the removal of the adhesion promoter.
  • the gas is preferably air or nitrogen, and more preferably air.
  • the removal of the adhesion promoter can be carried out, for example, in a gas-flowed oven or in a suitable drying apparatus, for example a belt dryer.
  • Oxidative dehydrogenation (oxydehydrogenation, ODH)
  • an oxidative dehydrogenation of n-butenes to butadiene is carried out by mixing an n-butenes containing starting gas mixture with an oxygen-containing gas and optionally additional inert gas or water vapor and is contacted in a fixed bed reactor at a temperature of 220 to 490 ° C with the arranged in a catalyst fixed bed catalyst.
  • the reaction temperature of the oxydehydrogenation is generally controlled by a heat exchange medium located around the reaction tubes.
  • liquid heat exchange agents e.g. Melting of salts such as potassium nitrate, potassium nitrite, sodium nitrite and / or sodium nitrate and melting of metals such as sodium, mercury and alloys of various metals into consideration. But ionic liquids or heat transfer oils are used.
  • the temperature of the heat exchange medium is between 220 to 490 ° C and preferably between 300 to 450 ° C and more preferably between 350 and 420 ° C.
  • the temperature in certain sections of the interior of the reactor during the reaction may be higher than that of the heat exchange medium, and a so-called hotspot is formed.
  • the location and height of the hotspot is determined by the reaction conditions, but it may also be regulated by the dilution ratio of the catalyst layer or the flow rate of mixed gas.
  • the oxydehydrogenation can be carried out in all fixed-bed reactors known from the prior art, such as, for example, in the hearth furnace, in the fixed bed tubular reactor or tube bundle reactor or in the plate heat exchanger reactor.
  • a tube bundle reactor is preferred.
  • the catalyst layer configured in the reactor may consist of a single layer or of two or more layers. These layers may consist of pure catalyst or be diluted with a material that does not react with the starting gas or components of the product gas of the reaction. Furthermore, the catalyst layers may consist of solid material or supported shell catalysts.
  • n-butenes 1, butene and / or cis- / trans-2-butene
  • a butene-containing gas mixture can be used. Such can be obtained, for example, by non-oxidative dehydrogenation of n-butane.
  • a fraction containing n-butenes (1-butene and / or 2-butene) as a main component and obtained from the C 4 fraction of naphtha cracking by separating butadiene and isobutene may be used.
  • gas mixtures which comprise pure 1-butene, cis-2-butene, trans-2-butene or mixtures thereof and which have been obtained by dimerization of ethylene can also be used as starting gas.
  • n-butenes containing gas mixtures obtained by catalytic fluid cracking can be used as the starting gas.
  • the starting gas mixture containing n-butenes is obtained by non-oxidative dehydrogenation of n-butane.
  • a non-oxidative catalytic dehydrogenation with the oxidative dehydrogenation of the n-butenes formed, a high yield of butadiene, based on n-butane used, can be obtained.
  • non-oxidative catalytic n-butane dehydrogenation a gas obtained in addition to butadiene, 1-butene, 2-butene and unreacted n-butane secondary constituents.
  • Common secondary constituents are hydrogen, water vapor, nitrogen, CO and CO2, methane, ethane, ethene, propane and propene.
  • the composition of the gas mixture leaving the first hydrogenation zone can vary greatly depending on the mode of operation of the dehydrogenation.
  • the product gas mixture has a comparatively high content of water vapor and carbon oxides.
  • the product gas mixture of the non-oxidative dehydrogenation has a comparatively high content of hydrogen.
  • the product gas stream of the non-oxidative n-butane dehydrogenation typically contains 0.1 to 15% by volume of butadiene, 1 to 15% by volume of 1-butene, 1 to 25% by volume of 2-butene (cis / trans) 2-butene), 20 to 70% by volume of n-butane, 1 to 70% by volume of steam, 0 to 10% by volume of low-boiling hydrocarbons (methane, ethane, ethene, propane and propene), 0.1 to 40% by volume of hydrogen, 0 to 70% by volume of nitrogen and 0 to 5% by volume of carbon oxides.
  • the product gas stream of the non-oxidative dehydrogenation can be fed to the oxidative dehydrogenation without further workup.
  • any impurities may be present in a range in which the effect of the present invention is not inhibited.
  • branched and unbranched hydrocarbons such as e.g. Methane, ethane, ethene, acetylene, propane, propene, propyne, n-butane, isobutane, isobutene, n-pentane, and dienes such as 1,2-butadiene.
  • the amounts of impurities are generally 70% or less, preferably 30% or less, more preferably 10% or less, and particularly preferably 1% or less.
  • the concentration of linear monoolefins having 4 or more carbon atoms (n-butenes and higher homologs) in the starting gas is not particularly limited; it is generally 35.00-99.99 vol.%, preferably 71.00-99.0 vol.%, and more preferably 75.00-95.0 vol.%.
  • a gas mixture which has a molar oxygen: n-butenes ratio of at least 0.5. Preference is given to operating at an oxygen: n-butenes ratio of 0.55 to 10.
  • the starting material gas can be mixed with oxygen or an oxygen-containing gas, for example air, and optionally additional inert gas or water vapor. The resulting oxygen-containing gas mixture is then fed to the oxydehydrogenation.
  • the molecular oxygen-containing gas is a gas which generally comprises more than 10% by volume, preferably more than 15% by volume, and more preferably more than 20% by volume of molecular oxygen, and specifically, it is preferably air.
  • the upper limit of the content of molecular oxygen is generally 50% by volume or less, preferably 30% by volume or less, and more preferably 25% by volume or less.
  • any inert gases may be present in a range in which the effect of the present invention is not inhibited.
  • a possible inert gas These can be called nitrogen, argon, neon, helium, CO, CO2 and water.
  • the amount of inert gases for nitrogen is generally 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. In the case of components other than nitrogen, it is generally 10% by volume or less, preferably 1% by volume or less. If this amount becomes too large, it becomes increasingly difficult to supply the reaction with the required oxygen.
  • inert gases such as nitrogen and also water (as water vapor) may be contained.
  • Nitrogen is present to adjust the oxygen concentration and to prevent the formation of an explosive gas mixture, the same applies to water vapor.
  • Water vapor is also present to control the coking of the catalyst and to dissipate the heat of reaction.
  • water (as water vapor) and nitrogen are mixed in the mixed gas and introduced into the reactor.
  • a proportion of 0.2-5.0 (parts by volume), preferably 0.5-4, and more preferably 0.8-2.5, based on the introduction amount of the above-mentioned starting gas is preferably introduced.
  • nitrogen gas into the reactor it is preferable to use a content of 0.1-8.0 (parts by volume), preferably 0.5-5.0, and more preferably 0.8-3.0, based on the introduction amount of the above Starting gas, initiated.
  • the content of the starting gas containing the hydrocarbons in the mixed gas is generally 4.0% by volume or more, preferably 6.0% by volume or more, and still more preferably 8.0% by volume or more.
  • the upper limit is 20 vol% or less, preferably 16.0 vol% or less, and more preferably 13.0 vol% or less.
  • the residence time in the reactor in the present invention is not particularly limited, but the lower limit is generally 0.3 s or more, preferably 0.7 s or more, and still more preferably 1.0 s or more.
  • the upper limit is 5.0 seconds or less, preferably 3.5 seconds or less, and more preferably 2.5 seconds or less.
  • the ratio of flow rate of mixed gas, based on the amount of catalyst inside the reactor, is 500-8000 hr.sup.- 1 , preferably 800-4000 hr.sup.- 1 and even more preferably 1200-3500.r.sup.- 1 .
  • the butene load of the catalyst (expressed in terms of (g catalyst * hour) is generally 0.1 -5.0 hl -1 , preferably 0.2-3.0 hl -1 , and even more preferably 0, in stable operation , 25-1, 0 hl -1 Volume and mass of the catalyst refer to the complete catalyst consisting of carrier and active mass. Regeneration of the multimetal oxide catalyst
  • a regeneration step (ii) is carried out between in each case two production steps (i).
  • the regeneration step (ii) is carried out before the loss of constant-temperature loss exceeds 25%.
  • the regeneration cycle (ii) is carried out by passing an oxygen-containing regeneration gas mixture at a temperature of 200 to 450 ° C over the fixed catalyst bed, whereby the carbon deposited on the multimetal oxide catalyst is burned off. According to the invention, 5 to 50% by weight of the carbon deposited on the catalyst is burned off per regeneration cycle (ii).
  • the oxygen-containing regeneration gas mixture used in the regeneration step (i) generally contains an oxygen-containing gas and additional inert gases, water vapor and / or hydrocarbons. In general, it contains 0.5 to 22% by volume, preferably 1 to 20% by volume and in particular 2 to 18% by volume of oxygen.
  • a preferred oxygen-containing gas present in the regeneration gas mixture is air.
  • inert gas, water vapor and / or hydrocarbons may additionally be added to the oxygen-containing gas.
  • Possible inert gases include nitrogen, argon, neon, helium, CO and CO2.
  • the amount of inert gases for nitrogen is generally 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. In the case of components other than nitrogen, it is generally 10% by volume or less, preferably 1% by volume or less.
  • the amount of oxygen-containing gas is selected so that the volume fraction of molecular oxygen in the regeneration gas mixture at the beginning of the regeneration 0 to 50%, preferably 0.5 to 22% and more preferably 1 to 10%.
  • the proportion of molecular oxygen can be increased in the course of regeneration.
  • water vapor may also be contained in the oxygen-containing regeneration gas mixture. Nitrogen is present to adjust the oxygen concentration, the same applies to water vapor. Water vapor may also be present to remove the heat of reaction and as a mild oxidizing agent for the removal of carbonaceous deposits.
  • water (as water vapor) and nitrogen are mixed into the regeneration gas mixture and introduced into the reactor.
  • steam is introduced into the reactor at the beginning of regeneration, preferably a volume fraction of from 0 to 50%, preferably from 0.5 to 22% and even more preferably from 1 to 10% is introduced.
  • the proportion of water vapor can be increased during the regeneration.
  • the amount of nitrogen is chosen so that the volume fraction of molecular nitrogen in the regeneration gas mixture at the beginning of the regeneration is 20 to 99%, preferably 50 to 98% and even more preferably 70 to 96%. The amount of nitrogen can become low in the course of regeneration.
  • the regeneration gas mixture may contain hydrocarbons. These may be mixed in addition to or instead of the inert gases.
  • the volume fraction of hydrocarbons Substances in the oxygen-containing regeneration gas mixture is generally less than 50%, preferably less than 10% and even more preferably less than 2%.
  • the hydrocarbons may include saturated and unsaturated, branched and unbranched hydrocarbons, such as methane, ethane, ethene, acetylene, propane, propene, propyne, n-butane, isobutane, n-butene, isobutene, n-pentane and dienes such as 1, 3-butadiene and 1, 2-butadiene. They contain in particular hydrocarbons which have no reactivity in the presence of oxygen under the regeneration conditions in the presence of the catalyst.
  • the residence time of the regeneration gas mixture in the reactor during regeneration is not particularly limited, but the lower limit is generally 0.3 s or more, preferably 0.7 s or more, and still more preferably 1.0 s or more.
  • the upper limit is 7.0 seconds or less, preferably 5.0 seconds or less, and still more preferably 3.5 seconds or less.
  • the ratio of flow rate of mixed gas based on the volume of catalyst in the reactor interior is 500 to 8000 hr 1, preferably from 600 to 4000 r. 1
  • the temperature of the heat exchange medium is between 220 to 490 ° C and preferably between 300 to 450 ° C and more preferably between 350 and 420 ° C. All temperatures mentioned above and below for the production steps (i) and regeneration steps (ii) refer to the temperature of the heat exchange medium at the inlet of the heat exchange medium at the reactor.
  • the temperature in the regeneration cycle (ii) is up to 20 ° C, more preferably up to 10 ° C higher than the temperature in the production cycle (i).
  • the temperature in the production cycle (i) above 350 ° C, more preferably above 360 ° C and in particular above 365 ° C, and is at most 420 ° C.
  • the temperatures mentioned refer to the temperature of the heat exchange medium at the inlet of the heat exchange medium at the reactor.
  • the product gas stream leaving the oxidative dehydrogenation of the production step contains, in addition to butadiene, generally still unconverted n-butane and isobutane, 2-butene and steam.
  • it generally contains carbon monoxide, carbon dioxide, oxygen, nitrogen, methane, ethane, ethene, propane and propene, optionally hydrogen and oxygen-containing hydrocarbons, so-called oxygenates.
  • it contains only small amounts of 1-butene and isobutene.
  • the product gas stream leaving the oxidative dehydrogenation can be 1 to 40% by volume of butadiene, 20 to 80% by volume of n-butane, 0 to 5% by volume of isobutane, 0.5 to 40% by volume of 2 Butene, 0 to 5 vol.% 1-butene, 0 to 70 vol.% Water vapor, 0 to 10 vol.% Low-boiling hydrocarbons (methane, ethane, ethene, propane and propene), 0 to 40 vol. -% hydrogen, 0 to 30 vol .-% oxygen, 0 to 70 vol .-% nitrogen, 0 to 10 vol .-% carbon oxides and 0 to 10 vol .-% oxygenates have.
  • Oxygenates may be, for example, formaldehyde, furan, acetic acid, maleic anhydride, formic acid, methacrolein, methacrylic acid, crotonaldehyde, Crotonic acid, propionic acid, acrylic acid, methyl vinyl ketone, styrene, benzaldehyde, benzoic acid, phthalic anhydride, fluorenone, anthraquinone and butyraldehyde.
  • oxygenates can further oligomerize and dehydrogenate on the catalyst surface and in the workup, forming deposits containing carbon, hydrogen and oxygen, hereinafter referred to as coke. These deposits can, for the purpose of cleaning and regeneration, lead to interruptions in the operation of the process and are therefore undesirable.
  • Typical coke precursors include styrene, fluorenone and anthraquinone.
  • the product gas stream at the reactor exit is characterized by a temperature near the temperature at the end of the catalyst bed.
  • the product gas stream is then brought to a temperature of 150-400 ° C, preferably 160-300 ° C, more preferably 170-250 ° C.
  • heat exchanger It is possible to isolate the conduit through which the product gas stream flows to maintain the temperature in the desired range, but use of a heat exchanger is preferred.
  • This heat exchanger system is arbitrary as long as the temperature of the product gas can be maintained at the desired level with this system.
  • a heat exchanger there may be mentioned spiral heat exchangers, plate heat exchangers, double tube heat exchangers, multi-tube heat exchangers, boiler spiral heat exchangers, shell-shell heat exchangers, liquid-liquid contact heat exchangers, air heat exchangers, direct-contact heat exchangers and finned tube heat exchangers.
  • the heat exchanger system should preferably have two or more heat exchangers. If two or more intended heat exchangers are arranged in parallel, and thus a distributed cooling of the product gas obtained in the heat exchangers is made possible, the amount of high-boiling by-products that accumulate in the heat exchangers, and thus their operating time can be extended. As an alternative to the above-mentioned method, the two or more intended heat exchangers may be arranged in parallel.
  • the product gas is supplied to one or more, but not all, heat exchanger and after a certain period of operation, these heat exchangers are replaced by other heat exchangers.
  • the cooling can be continued, a portion of the heat of reaction recovered and in parallel, the deposited in one of the heat exchangers high-boiling by-products can be removed.
  • a solvent as long as it is capable of dissolving the high-boiling by-products, can be used without restriction, and as examples thereof, an aromatic hydrocarbon solvent, e.g. Toluene, xylene, etc. as well as an alkaline aqueous solvent, e.g. the aqueous solution of sodium hydroxide.
  • a process step for removing residual oxygen from the product gas stream can be carried out.
  • the residual oxygen can have a disturbing effect insofar as it can cause butadiene peroxide formation in downstream process steps and can act as an initiator for polymerization reactions.
  • Unstabilized 1,3-butadiene can form dangerous butadiene peroxides in the presence of oxygen.
  • the peroxides are viscous liquids. Their density is higher than that of butadiene. Moreover, since they are only slightly soluble in liquid 1,3-butadiene, they settle on the bottoms of storage containers. Despite their relatively low chemical reactivity, the peroxides are very unstable compounds that can spontaneously decompose at temperatures between 85 and 110 ° C. A special danger exists in the high
  • the oxygen removal is carried out immediately after the oxidative dehydrogenation.
  • a catalytic combustion stage is carried out in which oxygen is reacted with hydrogen added in this stage in the presence of a catalyst. As a result, a reduction in the oxygen content is achieved down to a few traces.
  • the product gas of the 02 removal stage is now brought to an identical temperature level as has been described for the area behind the ODH reactor.
  • the cooling of the compressed gas is carried out with heat exchangers, which may for example be designed as a tube bundle, spiral or plate heat exchanger.
  • the dissipated heat is preferably used for heat integration in the process.
  • a large part of the high-boiling secondary components and the water can be separated from the product gas stream by cooling.
  • This separation is preferably carried out in a quench.
  • This quench can consist of one or more stages.
  • a method is used in which the product gas is brought directly into contact with the cooling medium and thereby cooled.
  • the cooling medium is not particularly limited, but it is preferable to use water or an alkaline aqueous solution.
  • a gas stream is obtained in which n-butane, 1-butene, 2-butenes, butadiene, optionally oxygen, hydrogen, water vapor, small amounts of methane, ethane, ethene, propane and propene, isobutane, carbon oxides and inert gases remain , Furthermore, traces of high-boiling components can remain in this product gas stream, which were not quantitatively separated in the quench.
  • the product gas stream from the quench is then compressed in at least one first compression stage and subsequently cooled, wherein at least one condensate stream comprising water condenses out and a gas stream containing n-butane, 1-butene, 2-butenes, butadiene, optionally hydrogen, water vapor, in small amounts of methane, ethane, ethene, propane and propene, isobutane, carbon oxides and inert gases, optionally oxygen and hydrogen remains.
  • the compression can be done in one or more stages. Overall, a pressure in the range of 1, 0 to 4.0 bar (absolute) is compressed to a pressure in the range of 3.5 to 20 bar (absolute).
  • the condensate stream can therefore also comprise a plurality of streams in the case of multistage compression.
  • the condensate stream is generally at least 80 wt .-%, preferably at least 90 wt .-% of water and also contains minor amounts of low boilers, C4 hydrocarbons, oxygenates and carbon oxides.
  • Suitable compressors are, for example, turbo, rotary piston and reciprocating compressors. The compressors can be driven, for example, with an electric motor, an expander or a gas or steam turbine. Typical compression ratios (outlet pressure: inlet pressure) per compressor stage are between 1, 5 and 3.0, depending on the design.
  • the cooling of the compressed gas is carried out with heat exchangers, which may for example be designed as a tube bundle, spiral or plate heat exchanger.
  • heat exchangers which may for example be designed as a tube bundle, spiral or plate heat exchanger.
  • coolant cooling water or heat transfer oils are used in the heat exchangers.
  • air cooling is preferably used using blowers.
  • the butadiene, butene, butane, inert gases and optionally carbon oxides, oxygen, hydrogen and low-boiling hydrocarbons (methane, ethane, ethene, propane, propene) and small amounts of oxygenates containing stream is fed as output stream of further treatment.
  • the separation of the low-boiling secondary constituents from the product gas stream can be carried out by customary separation processes such as distillation, rectification, membrane process, absorption or adsorption.
  • the product gas mixture optionally after cooling, for example in a heat exchanger, can be passed through a membrane which is usually designed as a tube and which is permeable only to molecular hydrogen.
  • the molecular hydrogen thus separated can be used at least partly in a hydrogenation or else be supplied to other utilization, for example used to generate electrical energy in fuel cells.
  • the carbon dioxide contained in the product gas stream can be separated by CO2 gas scrubbing.
  • the carbon dioxide gas scrubber may be preceded by a separate combustion stage in which carbon monoxide is selectively oxidized to carbon dioxide.
  • the non-condensable or low-boiling gas constituents such as hydrogen, oxygen, carbon oxides, the low-boiling hydrocarbons (methane, ethane, ethene, propane, propene) and inert gas, such as, if appropriate, nitrogen in an absorption / desorption Cycle separated by means of a high-boiling absorbent, wherein a C4 product gas stream is obtained, which consists essentially of the C4 hydrocarbons.
  • the C4 product gas stream is at least 80% by volume, preferably at least 90% by volume, particularly preferably at least 95% by volume, of the C4 hydrocarbons, essentially n-butane, 2-butene and buta - serve.
  • the product gas stream is brought into contact with an inert absorbent in an absorption stage after prior removal of water, and the C4 hydrocarbons are absorbed in the inert absorbent, with deposition of C4 hydrocarbons being carried out. Sorbent and the other gas components containing exhaust gas can be obtained. In a desorption step, the C4 hydrocarbons are released from the absorbent again.
  • the absorption stage can be carried out in any suitable absorption column known to the person skilled in the art. Absorption can be accomplished by simply passing the product gas stream through the absorbent. But it can also be done in columns or in rotational absorbers. It can be used in cocurrent, countercurrent or cross flow. Preferably, the absorption is carried out in countercurrent.
  • Suitable absorption columns are, for example, tray columns with bell, centrifugal and / or sieve bottom, columns with structured packings, for example sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 such as Mellapak® 250 Y, and packed columns.
  • structured packings for example sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 such as Mellapak® 250 Y, and packed columns.
  • trickle and spray towers graphite block absorbers, surface absorbers such as thick-film and thin-layer absorbers, as well as rotary columns, dishwashers, cross-flow scrubbers and rotary scrubbers are also suitable.
  • an absorption column is fed in the lower region of the butadiene, butene, butane, and / or nitrogen and optionally oxygen, hydrogen and / or carbon dioxide-containing material stream.
  • the solvent and optionally water-containing material stream is abandoned.
  • Inert absorbent used in the absorption stage are generally high-boiling non-polar solvents in which the C4-hydrocarbon mixture to be separated has a significantly higher solubility than the other gas constituents to be separated off.
  • Suitable absorbents are relatively nonpolar organic solvents, for example aliphatic Cs to Cis alkanes, or aromatic hydrocarbons, such as the paraffin-derived middle oil fractions, toluene or bulky groups, or mixtures of these solvents, such as 1,2-dimethyl phthalate may be added.
  • Suitable absorbers are also esters of benzoic acid and phthalic acid with straight-chain d-Cs-alkanols, as well as so-called heat transfer oils, such as biphenyl and diphenyl ether, their chlorinated derivatives and triaryl alkenes.
  • a suitable absorbent is a mixture of biphenyl and diphenyl ether, preferably in the azeotropic composition, for example, the commercially available Diphyl ®. Often, this solvent mixture contains di-methyl phthalate in an amount of 0.1 to 25 wt .-%.
  • Suitable absorbents are octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, heptadecanes and octadecanes, or fractions obtained from refinery streams containing as main components said linear alkanes.
  • the solvent used for the absorption is an alkane mixture such as tetradecane (technical C14-C17 cut).
  • an offgas stream is withdrawn, which is essentially inert gas, carbon oxides, optionally butane, butenes, such as 2-butenes and butadiene, optionally oxygen, hydrogen and low-boiling hydrocarbons (for example methane, ethane, ethene, propane, propene) and contains water vapor.
  • This stream can be partially fed to the ODH reactor or 02 removal reactor.
  • the inlet flow of the ODH reactor can be adjusted to the desired C4 hydrocarbon content.
  • the loaded with C4 hydrocarbons solvent stream is passed into a desorption column.
  • the desorption step is carried out by relaxation and / or heating of the loaded solvent.
  • the preferred process variant is the addition of stripping steam and / or the supply of live steam in the bottom of the desorber.
  • the solvent depleted of C4 hydrocarbons may be fed as a mixture together with the condensed vapor (water) to a phase separation, so that the water is separated from the solvent. All apparatuses known to the person skilled in the art are suitable for this purpose. It is also possible to use the separated water from the solvent to produce the stripping steam.
  • the absorbent regenerated in the desorption stage is returned to the absorption stage.
  • the separation is generally not quite complete, so that in the C4 product gas stream - depending on the type of separation - still small amounts or even traces of other gas components, in particular the heavy boiling hydrocarbons, may be present.
  • the volume flow reduction also caused by the separation relieves the subsequent process steps. Consisting essentially of n-butane, butenes, such as 2-butenes and butadiene.
  • Product gas stream generally contains 20 to 80% by volume of butadiene, 20 to 80% by volume of n-butane, 0 to 10% by volume of 1-butene, and 0 to 50% by volume of 2-butenes, the total amount 100% by volume. Furthermore, small amounts of iso-butane may be included.
  • the C4 product gas stream can then be separated by an extractive distillation into a stream consisting essentially of n-butane and 2-butene and a stream consisting of butadiene.
  • the stream consisting essentially of n-butane and 2-butene can be wholly or partly recycled to the C4 feed of the ODH reactor. Since the butene isomers of this recycle stream consist essentially of 2-butenes and these 2-butenes are generally dehydrogenated oxidatively slower to butadiene than 1-butene, this can be
  • the isomer distribution can be adjusted according to the isomer distribution present in the thermodynamic equilibrium.
  • the extractive distillation may, for example, as described in "petroleum and coal - natural gas - petrochemistry", Volume 34 (8), pages 343 to 346 or “Ullmann's Encyclopedia of Industrial Chemistry", Volume 9, 4th edition 1975, pages 1 to 18, be performed.
  • the C 4 - product gas stream with an extractant preferably an N-methylpyrrolidone
  • the extraction zone is generally carried out in the form of a wash column which contains trays, fillers or packings as internals. This generally has 30 to 70 theoretical plates, so that a sufficiently good release effect is achieved.
  • the wash column has a backwash zone in the column head. This backwash zone serves to recover the extractant contained in the gas phase by means of a liquid hydrocarbon reflux, for which purpose the top fraction is condensed beforehand.
  • the mass ratio of extractant to C 4 product gas stream in the feed of the extraction zone is generally from 10: 1 to 20: 1.
  • the extractive distillation is preferably carried out at a bottom temperature in the range from 100 to 250 ° C., in particular at a temperature in the range from 110 to 210 ° C, a head temperature in the range of 10 to 100 ° C, in particular in the range of 20 to 70 ° C and a pressure in the range of 1 to 15 bar, in particular operated in the range of 3 to 8 bar.
  • the extractive distillation column preferably has from 5 to 70 theoretical plates.
  • Suitable extractants are butyrolactone, nitriles such as acetonitrile, propionitrile, methoxypropionitrile, ketones such as acetone, furfural, N-alkyl-substituted lower aliphatic acid amides such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-formylmorpholine, N-alkyl-substituted cyclic acid amides (lactams) such as N Alkylpyrrolidones, especially N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • alkyl-substituted lower aliphatic acid amides or N-alkyl substituted cyclic acid amides are used.
  • Particularly advantageous are dimethylformamide, acetonitrile, furfural and in particular NMP.
  • mixtures of these extractants with each other e.g. NMP and acetonitrile, mixtures of these extractants with cosolvents and / or tert-butyl ether, e.g. Methyl tert-butyl ether, ethyl tert-butyl ether, propyl tert-butyl ether, n- or iso-butyl tert-butyl ether
  • NMP preferably in aqueous solution, preferably with 0 to 20 wt .-% water, particularly preferably with 7 to 10 wt .-% water, in particular with 8.3 wt .-% water.
  • the overhead product stream of the extractive distillation column contains essentially butane and butenes and in small amounts of butadiene and is taken off in gaseous or liquid form.
  • the stream consisting essentially of n-butane and 2-butene contains 50 to 100% by volume of n-butane, 0 to 50% by volume of 2-butene and 0 to 3% by volume of further constituents, such as isobutane.
  • a stream containing the extractant, water, butadiene and small amounts of butenes and butane is obtained, which is fed to a distillation column.
  • the extraction solution is transferred to a desorption zone, wherein the butadiene is desorbed from the extraction solution.
  • the desorption zone can be embodied, for example, in the form of a wash column which has 2 to 30, preferably 5 to 20 theoretical stages and optionally a backwashing zone with, for example, 4 theoretical stages.
  • This backwash zone is used to recover the extractant contained in the gas phase by means of a liquid hydrocarbon reflux, to which the top fraction is condensed beforehand.
  • a liquid hydrocarbon reflux to which the top fraction is condensed beforehand.
  • trays or packing are provided.
  • the distillation is preferably carried out at a bottom temperature in the range of 100 to 300 ° C, in particular in the range of 150 to 200 ° C and a top temperature in the range of 0 to 70 ° C, in particular in the range of 10 to 50 ° C.
  • the pressure in the distillation column is preferably in the range from 1 to 10 bar. In general, in the desorption zone, reduced pressure and / or elevated temperature prevails over the extraction zone.
  • the product stream obtained at the top of the column generally contains 90 to 100% by volume of butadiene, 0 to 10% by volume of 2-butene and 0 to 10% by volume of n-butane and isobutane.
  • a further distillation according to the prior art can be carried out.
  • the invention is further illustrated by the following examples.
  • the quantities conversion (X) and selectivity (S) calculated in the examples were determined as follows: mol Bute ⁇ ne g i U ⁇ times (ßute.ne ag
  • the original temperature was kept at 60 ° C.
  • the gas inlet temperature of the spray tower was 300 ° C, the gas outlet temperature 1 10 ° C.
  • the powder obtained had a particle size (d 50) of less than 40 ⁇ m.
  • the resulting powder was mixed with 1 wt .-% graphite, compacted twice with 9 bar pressure and crushed through a sieve with a mesh size of 0.8 mm.
  • the split was again mixed with 2% by weight of graphite and the mixture was pressed with a Kilian S100 tablet press into rings of 5 ⁇ 3 ⁇ 2 mm (outer diameter ⁇ length ⁇ inner diameter).
  • the catalyst precursor obtained was calcined in batches (500 g) in a convection oven from Heraeus, DE (type K, 750/2 S, internal volume 55 l). The following program was used for this:
  • Example 1 The calcined rings of Example 1 were ground to a powder.
  • Support bodies (steatite rings) with the dimensions 5 ⁇ 3 ⁇ 2 mm (outer diameter ⁇ height ⁇ inner diameter) were coated with this precursor material.
  • the drum was rotated (25 rpm).
  • About 60 ml of liquid binder (mixture glycerol: water 1: 3) were sprayed onto the support over a spray nozzle operated with compressed air for about 30 minutes (spray air 500 Nl / h).
  • the nozzle was installed in such a way that the spray cone wetted the carried in the drum carrier body in the upper half of the rolling distance.
  • the screening reactor was a salt bath reactor having a length of 120 cm and an inside diameter of 14.9 mm and a thermowell having an outside diameter of 3.17 mm.
  • the thermowell contained a multiple thermocouple with 7 measuring points.
  • the bottom 4 measuring points had a distance of 10 cm and the top 4 measuring points a distance of 5 cm.
  • Butane and raffinate II or 1-butene were dosed liquid at about 10 bar by a coriolis flow meter, mixed in a static mixer and then relaxed in a heated evaporator section and evaporated. This gas was then mixed with nitrogen and passed in a preheater with a steatite.
  • Example 3 On the catalyst chair at the bottom of the screening reactor, a 6 cm long bed was filled consisting of 16 g steatite balls with a diameter of 3.5-4.5 mm. Thereafter, 44 g of the catalyst from Example 1 were thoroughly mixed with 88 g of steatite rings of the same geometry and filled into the reactor (146 ml bulk volume, 88 cm bed height). The catalyst bed was followed by a 7 cm long feed consisting of 16 g of steatite balls with a diameter of 3.5-4.5 mm.
  • the reactor was operated with 200 NL / h of a reaction gas of the composition 8% 1-butene, 2% butane, 7.5% oxygen, 15% water, 67.5% nitrogen at a salt bath temperature of 330 ° C for 50 hours.
  • the product gases were analyzed by GC. The conversion and selectivity data are listed in Table 1.
  • a 6 cm long bed was filled consisting of 16 g steatite balls with a diameter of 3.5-4.5 mm.
  • 120 g of the catalyst from Example 2 were charged into the reactor (18 g of active mass, 13 ml bulk volume, 68 cm bed height).
  • the catalyst bed was followed by a 7 cm long feed consisting of 16 g of steatite balls with a diameter of 3.5-4.5 mm.
  • the reactor was charged with 200 NL / h of a reaction gas of the composition 8% by volume of 1-butene, 2% by volume of butane, 7.5% by volume of oxygen, 15% by volume of steam, 67.5% by volume. % Nitrogen operated at a salt bath temperature of 357 ° C for 50 hours. The product gases were analyzed by GC. The conversion and selectivity data are listed in Table 1. Thereafter, a mixture of 10 vol .-% oxygen, 80 vol .-% nitrogen and 10 vol .-% steam was passed over the catalyst for 20 hours and heated to 400 ° C. The resulting carbon oxides were recorded by means of an IR measuring device. The amount of burnt carbon is also listed in Table 1.
  • the catalyst was operated for an additional 20 hours with the gas described above. Thereafter, with gas of the composition, 10% by volume of oxygen, 10% by volume of steam and 90% by volume of nitrogen were purged while simultaneously raising the temperature to 400 ° C to determine the amount of total carbon deposited.
  • the amount of burnt carbon is shown in Table 2.
  • the reactor was charged with 200 NL / h of a reaction gas of the composition 8% by volume of butene, 2% by volume of butane, 7.5% by volume of oxygen, 15% by volume of steam, 67.5% by volume of nitrogen operated at a salt bath temperature of 348 ° C for 20 hours (per production step).
  • the product gases were analyzed by GC.
  • the conversion and selectivity data are listed in Table 3.
  • the catalyst was operated for an additional 20 hours with the gas described above. Thereafter, with gas of the composition, 10% by volume of oxygen, 10% by volume of steam and 90% by volume of nitrogen were purged while simultaneously raising the temperature to 400 ° C to determine the amount of total carbon deposited.
  • the amount of burnt carbon is shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de déshydrogénation oxydative de n-butènes en butadiène, comprenant deux ou plusieurs étapes de production (i) et au moins une étape de régénération (ii), procédé dans lequel (i) dans une étape de production, un mélange de gaz de départ contenant des n-butènes est mélangé à un gaz contenant de l'oxygène et, dans un réacteur à lit fixe à une température de 220 à 490 °C, est amené en contact avec un catalyseur à oxyde multimétallique disposé dans un lit fixe de catalyseur, contenant au moins du molybdène et un autre métal et, avant que la perte de rendement à température constante ne dépasse 25 %, (ii) dans une étape de régénération, le catalyseur à oxyde multimétallique est régénéré par le passage par-dessus le lit fixe à catalyseur d'un gaz de régénération oxygéné à une température de 200 à 450 °C et par la combustion du carbone déposé sur le catalyseur, sachant qu'entre deux étapes de production (i) est effectuée une étape de régénération (ii), caractérisé en ce que par étape de régénération (ii) 2 à 50 % en poids du carbone déposé sur le catalyseur sont brûlés.
EP13798701.2A 2012-12-06 2013-12-03 Procédé de déshydrogénation oxydative de n-butènes en butadiène Withdrawn EP2950928A1 (fr)

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PCT/EP2013/075361 WO2014086768A1 (fr) 2012-12-06 2013-12-03 Procédé de déshydrogénation oxydative de n-butènes en butadiène
EP13798701.2A EP2950928A1 (fr) 2012-12-06 2013-12-03 Procédé de déshydrogénation oxydative de n-butènes en butadiène

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KR20150105457A (ko) * 2013-01-15 2015-09-16 바스프 에스이 n-부텐을 부타디엔으로 산화성 탈수소화시키는 방법
CN107750189A (zh) * 2015-06-29 2018-03-02 Smh有限公司 烃进料的转化方法
US20190299195A1 (en) * 2015-12-25 2019-10-03 Nippon Kayaku Kabushiki Kaisha Method for regenerating catalyst for butadiene production
CN105597782B (zh) * 2016-01-28 2018-06-26 惠生工程（中国）有限公司 一种丁烯氧化脱氢制丁二烯绝热固定床催化剂的再生方法
JP2017149655A (ja) * 2016-02-22 2017-08-31 日本化薬株式会社 共役ジオレフィンの製造方法
JP2017149654A (ja) * 2016-02-22 2017-08-31 日本化薬株式会社 共役ジオレフィンの製造方法
CN114213207B (zh) * 2021-12-14 2024-04-19 润和催化剂股份有限公司 一种丙烷脱氢集成水煤气反应的工艺方法及其装置系统

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CN104837558A (zh) 2015-08-12
WO2014086768A1 (fr) 2014-06-12
EA201591040A1 (ru) 2015-11-30
WO2014086768A8 (fr) 2015-10-22
KR20150094620A (ko) 2015-08-19

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