EP2928603A1 - Verfahren zur oxidativen dehydrierung von n-butenen zu butadien - Google Patents

Verfahren zur oxidativen dehydrierung von n-butenen zu butadien

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Publication number
EP2928603A1
EP2928603A1 EP13814454.8A EP13814454A EP2928603A1 EP 2928603 A1 EP2928603 A1 EP 2928603A1 EP 13814454 A EP13814454 A EP 13814454A EP 2928603 A1 EP2928603 A1 EP 2928603A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
butenes
butadiene
gas
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13814454.8A
Other languages
German (de)
English (en)
French (fr)
Inventor
Philipp GRÜNE
Wolfgang RÜTTINGER
Oliver HAMMEN
Christian Walsdorff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP13814454.8A priority Critical patent/EP2928603A1/de
Publication of EP2928603A1 publication Critical patent/EP2928603A1/de
Withdrawn legal-status Critical Current

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    • 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
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    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
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    • B01J37/033—Using Hydrolysis
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    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
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    • B01J37/08—Heat treatment
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    • 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
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    • 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
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    • C07C2523/32—Manganese, technetium or rhenium
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    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
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    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
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    • C07C2523/755—Nickel
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • the invention relates to a catalyst, in particular a coated catalyst for the oxidative dehydrogenation of n-butenes to butadiene, to its use and 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 rubbers).
  • thermoplastic terpolymers acrylonitrile-butadiene-styrene copolymers
  • Butadiene is further converted to sulfolane, chloroprene and 1, 4-hexamethylenediamine (over 1, 4-dichlorobutene and adiponitrile).
  • sulfolane sulfolane
  • chloroprene 1, 4-hexamethylenediamine
  • 4-dichlorobutene and adiponitrile By 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.
  • WO2005 / 063658 discloses a process for producing butadiene from n-butane by the steps
  • This process is characterized by a particularly effective utilization of raw materials. Thus, losses of the raw material n-butane are minimized by recycling unreacted n-butane into the dehydrogenation.
  • the coupling of non-oxidative catalytic dehydrogenation and oxidative dehydrogenation achieves a high butadiene yield.
  • the process is characterized by high selectivity as compared to the production of butadiene by cracking. There are no by-products. It eliminates the costly separation of butadiene from the product gas mixture of the cracking process.
  • 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 which is determined on the assumption of charge neutrality by the valency and frequency of the elements other than oxygen, and (ii) at least one pore-forming agent.
  • Steatite balls with a diameter of 2 to 3 mm are used as carrier bodies for the coated catalysts.
  • WO 2010/137595 discloses a multimetal oxide catalyst for the oxidative dehydrogenation of alkenes to dienes comprising at least molybdenum, bismuth and cobalt, of the general formula
  • 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, which can eventually lead to coking and deactivation of the catalyst and to deposits and blockages in pipes and components behind the oxydehydrogenation reactor (ODH reactor).
  • coke precursors are, for example, styrene, anthraquinone and fluorenone.
  • the object of the invention is to provide a process for the oxidative dehydrogenation of n-butenes to butadiene, in which less coke precursors are formed.
  • a catalyst which is obtainable from a catalyst precursor comprising a catalytically active, molybdenum and at least one further metal-containing multimetal oxide of the general formula (I) Moi2BiaFebCOcNidCr e X 1 fX 2 gOx which has the following meaning:
  • 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;
  • x a number determined by the valence and frequency of the elements other than oxygen in (I); characterized in that the catalyst is in the form of a hollow cylinder, wherein the inner diameter is 0.2 to 0.8 times the outer diameter and the length is 0.5 to 2.5 times the outer diameter, and that the catalyst precursor is not a pore-forming agent contains.
  • coke precursors are pressure dependent.
  • the formation of certain coke precursors such as styrene, anthraquinone and fluorenone increases at pressures at the reactor inlet above 1, 3 bar absolutely disproportionately strong.
  • the catalysts used in the invention have a particularly low pressure drop, so that the total oxidative dehydrogenation can be carried out at a lower pressure.
  • the use of pore formers can improve the transport properties in the catalyst grain.
  • the conditions of the thermal aftertreatment must be closely monitored to prevent too rapid decomposition of the pore-forming agent.
  • the abrasion resistance of a catalyst can be greatly reduced by the use of a pore-forming agent. Attrition of the catalyst can accumulate in the reactor bed causing a large increase in pressure loss.
  • the catalyst according to the invention may be a solid 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 oxide of the general formula (I).
  • the shell (b) of the catalyst precursor contains no pore-forming agent.
  • Preferred catalysts have the dimensions outside diameter x inside diameter x length (4 to 10 mm) x (2 to 8 mm) x (2 to 10 mm). Particularly preferred catalysts have the dimensions outside diameter x inside diameter x length (5 to 8 mm) x (3 to 5 mm) x (2 to 6 mm).
  • the support body (a) preferably has the dimensions outside diameter x inside diameter x length (4 to 10 mm) x (2 to 8 mm) x (2 to 10 mm).
  • the carrier body has the dimensions outer diameter x inner diameter x length (5 to 8 mm) x (3 to 5 mm) x (2 to 6 mm).
  • the layer thickness D of the shell (b) of a molybdenum and at least one further metal-containing multimetal oxide mass is generally from 5 to 1000 ⁇ m. Preferred are 10 to 800 ⁇ , more preferably 50 to 600 ⁇ and most preferably 80 to 500 ⁇ .
  • the cross-sectional loading indicates the mass flow of educt gas relative to the cross-sectional area of the reactor tubes.
  • the cross-sectional load is usually 1 -5 kg / (m 2 s) and the pressure loss 20-400 mbar per meter of bed length.
  • a bed of catalyst At a cross-sectional load of 3 kg / (m 2 s), a bed length of 5 m and a gas velocity of 2 m / s, a bed of catalyst generally has a pressure drop of 100 to 2000 mbar, preferably from 250 to 1500 mbar and more preferably from 350 to 1000 mbar.
  • the quotient f / dp is then generally 333-6667 nr 1 , preferably 833-5000 nr 1 and even more preferably 1 167-3333 nr 1 .
  • 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. In a further preferred embodiment, the multimetal oxide contains chromium. In a further preferred embodiment, the multimetal oxide contains manganese.
  • 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 Pat. No. 4,547,615 (Moi2BiFeo, i Ni 8 ZrCr3Ko, 2 Ox and Moi2BiFeo, i Ni 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 the Range 6 S c + ds 8.
  • the stoichiometric coefficient e is preferably in the range 0.1 ⁇ e S 2, and particularly preferably in the range 0.2 ⁇ e ⁇ 1.
  • the stoichiometric coefficient g is suitably> 0.
  • Coated catalysts according to the invention with catalytically active oxide compositions whose molar ratio of Co / Ni is at least 2: 1, preferably at least 3: 1 and particularly preferably at least 4: 1, are advantageous. The best is only Co.
  • the coated catalyst is prepared by applying to the support by means of a binder a layer containing the molybdenum and at least one further metal-containing multimetal, drying the coated support (shell catalyst precursor) dry and thermally treated.
  • the multimetal oxide containing layer of the shell catalyst precursor does not contain pore formers such as malonic acid, melamine, nonylphenol ethoxylate, stearic acid, glucose, starch, fumaric acid and succinic acid prior to the final thermal treatment.
  • pore formers such as malonic acid, melamine, nonylphenol ethoxylate, stearic acid, glucose, starch, fumaric acid and succinic acid prior to the final thermal treatment.
  • finely divided, molybdenum and at least one further metal-containing multimetal oxides are basically obtainable by producing an intimate dry mixture of starting compounds of the elemental constituents of the catalytically active oxide composition and the intimate dry mixture calcined at a temperature of 150 to 650 ° C.
  • suitable finely divided multimetal oxide compositions For the preparation of suitable finely divided multimetal oxide compositions one starts from known starting compounds of the elemental constituents of the desired multimetal oxide composition in the respective stoichiometric ratio, and produces as intimately as possible, preferably finely divided, dry mixture, which is then subjected to a thermal treatment (calcination) ,
  • 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.
  • Suitable shaping aids are, for example, water, boron trifluoride or graphite.
  • lubricants are, for example, water, boron trifluoride or graphite.
  • 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 .-%.
  • Slip aid preferred according to the invention is graphite.
  • the calcination of the Katalysatorvortechnikvortechnikrform stresses is usually carried out at temperatures exceeding 350 ° C. Normally, however, 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 temperature of 380 ° C. advantageously the temperature of 400 ° C., with particular advantage the temperature of 420 ° C. and very particularly preferably the temperature of 440 ° C. exceeded.
  • the thermal treatment can be used in its temporal chen process also be divided into several sections.
  • a thermal treatment at a temperature of 150 to 350 ° C, preferably from 220 to 280 ° C, and then a thermal treatment at a temperature of 400 to 600 ° C, preferably from 430 to 550 ° C are performed.
  • 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 calcination of the catalyst precursor moldings may be carried out both under inert gas and under an oxidative atmosphere, e.g. Air (mixture of inert gas and oxygen) and also under reducing atmosphere (for example mixture of inert gas, NH 3, CO and / or H 2 or methane).
  • an oxidative atmosphere e.g. Air (mixture of inert gas and oxygen) and also under reducing atmosphere (for example mixture of inert gas, NH 3, CO and / or H 2 or methane).
  • the thermal treatment can also be carried out under vacuum.
  • the thermal treatment of the catalyst precursor moldings in a variety of furnace types such. heated Um Kunststoffsch, Hordenöfen, rotary kilns, belt calciner 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 multimetal oxide composition may contain chromium oxide.
  • suitable starting materials are, in particular, halides, nitrates, formates, oxalates, acetates, carbonates and / or hydroxides.
  • the thermal decomposition of chromium (III) compounds to chromium (III) oxide occurs independently of the presence or absence of oxygen, mainly between 70-430 ° C over several chromium (VI) -containing intermediates (see, for example, J. Therm. Anal. Cal., 72, 2003, 135 and Env. See, Tech. 47, 2013, 5858).
  • chromium (VI) oxide is not required for the catalytic oxydehydrogenation of alkenes to dienes, especially butenes to butadiene. Due to the toxicity and environmental harmfulness of Cr (VI) oxide, the active composition should therefore be substantially free of chromium (VI) oxide.
  • Chromium (VI) oxide content largely depends on calcination conditions, in particular the highest temperature in the calcination step and of its holding time. Here, the higher the temperature is and the longer the holding time, the lower the content of chromium (VI) oxide.
  • the obtained from the calcination shaped body of catalytically active multimetal oxide can be used as a solid catalyst.
  • the shaped body of multimetal oxide composition can furthermore be converted by grinding into a finely divided powder for the preparation of a shell catalyst, which is then applied to the outer surface with the aid of a liquid binder a carrier body can be applied.
  • the fineness of the catalytically active oxide mass to be applied to the surface of the carrier body is of course adapted to the desired shell thickness. Production of coated catalysts
  • Suitable carrier materials for shell-type catalysts according to the invention 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 5 to 8 mm and a wall thickness of 1 to 2 mm.
  • An example are rings of geometry 7 mm ⁇ 4 mm ⁇ 3 mm (outer diameter ⁇ inner diameter ⁇ length) as the carrier body.
  • the layer thickness D of a molybdenum and at least one further metal containing Muletetalloxidmasse is usually from 5 to 1000 ⁇ . Preference is given to 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 masses are applied to the surface of the carrier body 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 5 to 50% by weight and more preferably from 8 to 30% by weight.
  • 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 by dispersing the finely divided mass of molybdenum-containing multimetal oxide dispersed in the liquid binder and spraying the resulting suspension on moving and optionally 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 coated catalysts can be reduced.
  • 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 carrier 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 rotating rotary container guides the hollow-cylindrical carrier bodies under two metering devices arranged at a certain distance one after the other.
  • the first of the two metering devices is expediently a nozzle, through which the carrier bodies rolling in the rotating turntable are sprayed with the liquid binder to be used and moistened in a controlled manner.
  • the second metering device is located outside of the atomizing cone of the sprayed liquid binder and serves to supply the finely divided mass, for example via a vibrating trough.
  • the controlled moistened carrier body absorb the supplied active powder, which compacts by the rolling motion on the outer surface of the cylindrical carrier body to form a coherent shell.
  • the base body coated in this way again passes through the spray nozzle in the course of the subsequent revolution, being moisturized in a controlled manner in order to terschul another layer of finely divided mass to be able to accommodate, etc.
  • An intermediate drying is not required in the rule.
  • the removal of the liquid binder may take place, partially or completely, by the final supply of heat, for example by the action of hot gases, such as N 2 or air.
  • hot gases such as N 2 or air.
  • 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 to the stated temperature between 0.5 and 24 hours in order to remove the adhesion promoter.
  • 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)
  • the present invention also provides for the use of the solid material catalysts and shell catalysts according to the invention in a process for the oxidative dehydrogenation of 1-butene and / or 2-butene to butadiene.
  • the catalysts according to the invention are notable for high activity, but in particular also for high selectivity with regard to the formation of 1,3-butadiene from 1-butene and 2-butene.
  • the invention also provides a process for the oxidative dehydrogenation of n-butenes to butadiene, in which a n-butenes containing starting gas mixture mixed with an oxygen-containing gas and optionally additional inert gas or water vapor and in a fixed bed reactor at a temperature of 220 to 490 ° C.
  • X 2 Li, Na, K, Cs and / or Rb,
  • a 0.4 to 5, preferably 0.5 to 2;
  • b 0 to 5, preferably 2 to 4;
  • c 0 to 10, preferably 3 to 10;
  • e 0 to 10, preferably 0.1 to 4;
  • f 0 to 24, preferably 0.1 to 2;
  • g 0 to 2, preferably 0.01 to 1;
  • x a number determined by the valence and frequency of the elements other than oxygen in (I); characterized in that the catalyst is in the form of a hollow cylinder, wherein the inner diameter is 0.2 to 0.8 times the outer diameter and the length is 0.5 to 2.5 times the outer diameter, and that the catalyst precursor contains no pore-forming agent.
  • the solid material and shell catalysts used according to the invention are characterized by a low pressure loss. This allows the oxidative dehydrogenation to be operated at a low pressure, thereby counteracting the formation of coke precursors and coke deposits on the catalyst and work-up.
  • the reactor inlet pressure is ⁇ 3 bar (g), preferably ⁇ 2 bar (g) and more preferably ⁇ 1, 5 (g) bar.
  • the reactor outlet pressure is ⁇ 2.8 bar (g), preferably ⁇ 1.8 bar (g) and more preferably ⁇ 1.3 (g) bar. The higher this value is, the greater the space-time yield of the reaction can be because a larger amount of reaction gas can be introduced into the reactor.
  • the reactor inlet pressure is at least 0.01 bar (g), preferably at least 0.1 bar (g) and more preferably 0.5 bar (g).
  • the reactor outlet pressure is at least 0.01 bar (g), preferably at least 0.1 bar (g) and more preferably 0.2 bar (g). The lower the value, the lower the formation of coke precursors and coke deposits on the catalyst and work-up.
  • the pressure loss over the entire catalyst bed is generally 0.01 to 2 bar (g), preferably 0.1 to 1, 5 bar, more preferably 0.4 to 1, 0 bar.
  • the reaction temperature of the oxydehydrogenation is generally controlled by a heat exchange medium located around the reaction tubes.
  • liquid heat exchange agents come z.
  • ionic liquids or Heat transfer oils can be 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 difference between hotspot temperature and the temperature of the heat exchange medium is generally between 1 -150 ° C, preferably between 10-100 ° C and more preferably between 20-80 ° C.
  • the temperature at the end of the catalyst bed is generally between 0-100 ° C, preferably between 0.1-50 ° C, more preferably between 1 -25 ° C above the temperature of the heat exchange medium.
  • 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 tube or tubular reactor or in the plate heat exchanger reactor.
  • a tube bundle reactor is preferred.
  • the oxidative dehydrogenation is carried out using the catalysts of the invention in fixed bed tubular reactors or fixed bed bundle reactors.
  • the reaction tubes are (as well as the other elements of the tube bundle reactor) usually made of steel.
  • the wall thickness of the reaction tubes is typically 1 to 3 mm. Their inner diameter is usually (uniformly) at 10 to 50 mm or 15 to 40 mm, often 20 to 30 mm.
  • the number of reaction tubes accommodated in the tube bundle reactor is generally at least 1000, or 3000, or 5000, preferably at least 10,000. Frequently, the number of reaction tubes accommodated in the tube bundle reactor is 15,000 to 30,000 or 40,000 or 50 000. Tube bundle reactors with a number of reaction tubes above 50,000 tend to be the exception.
  • the length of the reaction tubes normally extends to a few meters, typical is a reaction tube length in the range of 1 to 8 m, often 2 to 7 m, often 2.5 to 6 m.
  • thermal tubes serve primarily for the purpose of monitoring and controlling the reaction temperature along the reaction tubes, representative of all working tubes.
  • the thermal tubes normally contain, in addition to the fixed catalyst bed, a thermal sleeve fed only with a temperature sensor and centered therethrough in the thermal tube.
  • the number of thermal tubes in a tube bundle reactor is much smaller than the number of working tubes. Normally, the number of thermal tubes is ⁇ 20.
  • the catalyst layer configured in the reactor as described above may consist of a single layer or of 2 or more layers. These layers may be pure catalyst or diluted with a material that does not react with the source gas or components of the product gas of the reaction.
  • 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. It is also possible to use a fraction containing n-butenes (1-butene and / or 2-butene) as the main component and from the C 4 fraction of naphtha cracking by separating butadiene and isobutene.
  • 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.
  • n-butane dehydrogenation a gas mixture is obtained which, in addition to butadiene 1-butene, 2-butene and unreacted n-butane, contains minor constituents. Common secondary constituents are hydrogen, water vapor, nitrogen, CO and CO2, methane, ethane, ethene, propane and propene.
  • the composition of the gaseous mixture leaving the first dehydrogenation zone can vary widely depending on the mode of 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 exist in a range in which the effect of the present invention is not inhibited be.
  • n-butenes (1-butene and cis- / trans-2-butene)
  • impurities saturated and unsaturated, branched and unbranched hydrocarbons such.
  • methane, ethane, ethene, acetylene, propane, propene, propyne, n-butane, isobutane, isobutene, n-pentane and dienes such as 1, 2-butadiene may be mentioned.
  • the amounts of impurities are generally 70% or less, preferably 30% or less, more preferably 10% or less, and most 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, if appropriate, additional inert gas or steam. The resulting oxygen-containing gas mixture is then fed to the oxydehydrogenation.
  • the molecular oxygen-containing gas of the present invention is a gas generally comprising 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. Possible inert gases include 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 (by volume), preferably 0.5-4, and more preferably 0.8-2.5, based on the introduction amount of the aforementioned starting gas is preferably introduced.
  • preference is given to a proportion of 0.1-8.0 (volume fraction), preferably 0.5-5.0, and more preferably 0.8-3.0 based on the introduction amount of the aforementioned starting gas.
  • 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 hr.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
  • the volume and mass of the catalyst refer to the complete catalyst consisting of support and active mass
  • the volume change factor describes the flow difference from reactor inlet to outlet and is based on the flow rate of starting gas at the reactor inlet and the flow rate of product gas on It is expedient to determine it by the ratio of the volume concentration of an inert constituent, ie a constituent which is not reacted in any form in the reactor (for example Ar or N 2), of the reaction gas at the reactor inlet and reactor outlet , 15, preferably 1 - 1, 1, and particularly preferably 1, 01 -1, 08 amount.
  • the product gas stream leaving the oxidative dehydrogenation generally contains, in addition to butadiene, still unreacted n-butane and iso-butane, 2-butene and water vapor. As minor constituents it generally contains carbon monoxide, carbon dioxide, oxygen, nitrogen, methane, ethane, ethene, propane and propene, optionally hydrogen and oxygen-containing hydrocarbons, so-called oxygenates. In general, 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% by volume of 1-butene, 0 to 70% by volume of steam, 0 to 10% by volume of low-boiling hydrocarbons (methane, ethane, ethene, propane and propene), 0 to 40% by volume of hydrogen, 0 up to 30 vol.% oxygen, 0 to 70 vol.% nitrogen, 0 to 10 vol.% carbon oxides and 0 to 10 vol.% oxygenates.
  • 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% by volume of 1-butene, 0 to 70% by volume of steam, 0 to 10% by volume of low-bo
  • 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 exchangers, which are replaced after a certain period of operation of 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, such as an aromatic hydrocarbon solvent may be used.
  • an aromatic hydrocarbon solvent such as an aromatic hydrocarbon solvent may be used.
  • toluene, xylene, etc. and an alkaline aqueous solvent, such as.
  • the aqueous solution of sodium hydroxide can be used. If the product gas stream contains more than just traces of oxygen, a process step can be used to remove residual oxygen from the product gas stream.
  • 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 for this purpose, 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 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 preferably, water or an alkaline aqueous solution is used.
  • the cooling temperature of the product gas differs depending on the type of temperature of the product gas obtained from the reactor outlet and the cooling medium. In general, depending on the presence and temperature level of a heat exchanger, the product gas can reach a temperature of 100-440 ° C., preferably 140-300 ° C., particularly preferably 170-240 ° C., before the quench inlet.
  • the product gas inlet into the quench must be designed to minimize or prevent clogging due to deposits on and directly in front of the gas inlet.
  • the product gas is brought into contact with the cooling medium in the 1st quench stage. In this case, the cooling medium can be introduced through a nozzle in order to achieve the most efficient possible mixing with the product gas.
  • the quench stage can be used in the quench stage.
  • the coolant inlet into the quench must be designed to minimize or prevent clogging by deposits near the coolant inlet.
  • the product gas in the first quenching stage is cooled to 5-180 ° C, preferably to 30-130 ° C and even more preferably to 60-90 ° C.
  • the temperature of the coolant medium at the inlet may generally be 25-200 ° C, preferably 40-120 ° C, particularly preferably 50-90 ° C.
  • the pressure in the first quenching step is not particularly limited, but is generally 0.01 to 4 bar (g), preferably 0.1 to 2 bar (g), and more preferably 0.2 to 1 bar (g).
  • the cooling medium used in the cooling tower is often used in a circulating manner, which can lead to blockages due to solid precipitation if the production of conjugated dienes continues continuously.
  • the recycle stream of the cooling medium in liters per hour based on the mass flow of butadiene in grams per hour can generally be 0.0001 -5 l / g, preferably 0.001-1 l / g and particularly preferably 0.002-0.2 l / g.
  • the redemption of by-products of the ODH reaction, for example acetic acid, MSA, etc. in a cooling medium such as water is better at elevated pH than at low pH. Since the dissolution of by-products such as the above-mentioned pH of, for example, water lowers, the pH can be kept constant or increased by adding an alkaline medium. In general, the pH in the bottom of the first quenching stage is maintained between 2-14, preferably between 3-13, more preferably between 4-12.
  • the temperature of the cooling medium in the bottom can generally be 27-210.degree. C., preferably 45-130.degree. C., particularly preferably 55-95.degree. Since the loading of the cooling medium with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn from circulation and the circulating volume can be kept constant by adding unladen cooling medium.
  • the ratio of effluent amount and added amount depends on the vapor loading of the product gas and the product gas temperature at the end of the first quenching stage. When the cooling medium is water, the amount of addition in the first quenching stage is generally lower than the discharge amount.
  • the cooled and depleted in secondary components product gas stream can now be fed to a second quenching stage. In this he can now be brought into contact again with a cooling medium.
  • the product gas is cooled to 5-100 ° C, preferably 15-85 ° C and even more preferably 30-70 ° C, to the gas exit of the second quench stage.
  • the cooling Medium can be supplied in countercurrent to the product gas.
  • the temperature of the coolant medium at the coolant inlet may be 5-100 ° C, preferably 15-85 ° C, particularly preferably 30-70 ° C.
  • the pressure in the second quenching stage is not particularly limited, but is generally 0.01 to 4 bar (g), preferably 0.1 to 2 bar (g), and more preferably 0.2 to 1 bar (g).
  • the cooling medium used in the cooling tower is often used in a circulating manner so that blockages due to solid precipitation can occur if the production of conjugated dienes is continued continuously.
  • the recycle flow of the cooling medium in liters per hour based on the mass flow of butadiene in grams per hour may generally be 0.0001 -5 l / g, preferably 0.0001 -1 l / g and more preferably 0.002-0.2 l / g.
  • the redemption of by-products of the ODH reaction, for example acetic acid, MSA, etc. in a cooling medium such as water is better at elevated pH than at low pH.
  • the pH can be kept constant or increased by adding an alkaline medium.
  • the pH in the bottom of the second quenching stage is kept between 1 and 14, preferably between 2 and 12, particularly preferably between 3 and 1.
  • the more basic the better the redemption of some by-products.
  • very high pH values lead to the dissolution of by-products such as CO2 and thus to a very high consumption of the alkaline medium.
  • the temperature of the cooling medium in the bottom can generally be 20-210 ° C., preferably 35-120 ° C., particularly preferably 45-85 ° C. Since the loading of the cooling medium with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn from circulation and the circulating amount can be kept constant by adding unladen cooling medium.
  • the ratio of effluent amount and addition amount depends on the vapor loading of the product gas and the product gas temperature at the end of the first quenching stage. When the cooling medium is water, the amount of addition in the first quenching stage is generally larger than the discharge amount.
  • internals in the second quenching stage may be present.
  • Such internals include, for example, bell, centrifugal and / or sieve trays, structured packing columns, e.g. B.
  • Sheet metal packings with a specific surface area of 100 to 1000 m2 / m3 such as Mellapak® 250 Y, and packed columns.
  • the cycles of the two quench stages can be both separated from each other and also connected to each other.
  • the desired temperature of the circulating streams can be adjusted by means of suitable heat exchangers.
  • suitable structural measures such as the installation of a demister, can be taken.
  • high-boiling substances which are not separated from the product gas in the quench by further structural measures, such as gas Washes, are removed from the product gas.
  • 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 compressed in at least one first compression stage and subsequently cooled, with at least one condensate stream comprising water condensing out and a gas stream containing n-butane, 1-butene, 2-butenes, butadiene, optionally hydrogen, water vapor, in small amounts Methane, ethane, ethene, propane and propene, iso-butane, 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.
  • 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, membrane process, absorption or adsorption.
  • the product gas mixture can be passed through a membrane which is generally designed as a tube and which is permeable only to molecular hydrogen.
  • the thus separated molecular hydrogen can be used, if necessary, at least partially in a dehydrogenation or other recycling be supplied, for example, be 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 easily 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 consists of at least 80% by volume, preferably at least 90% by volume, more preferably at least 95% by volume, of the C4 hydrocarbons, essentially n-butane, 2-butene and butadiene.
  • the product gas stream after prior removal of water is contacted with an inert absorbent and the C4 hydrocarbons are absorbed in the inert absorbent, wherein C4 hydrocarbons laden absorbent and the other gas constituents containing exhaust gas are obtained.
  • 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 z. B.
  • tray columns with bell, centrifugal and / or sieve tray columns with structured packings, eg. B. Sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak® 250 Y, and packed columns.
  • structured packings eg. B. Sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 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 adsorbents used in the absorption stage are generally high-boiling non-polar solvents in which the C4-hydrocarbon mixture to be separated off has a pronounced lent higher solubility than the other gas components 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, examples game as 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, which contain the linear alkanes as main components.
  • 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.
  • the C 4 product gas stream consisting essentially of n-butane, butenes, such as 2-butenes and butadiene generally contains from 20 to 80% by volume of butadiene, from 20 to 80% by volume of n-butane, from 0 to 10% by volume. % 1 -butene, and 0 to 50% by volume of 2-butenes, the total amount being 100% by volume. Furthermore, small amounts of iso-butane may be included.
  • the C 4 product gas stream may 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 C 4 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 recycle stream may undergo a catalytic isomerization process prior to delivery to the ODH reactor. In this catalytic process, 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 washing column in the column head preferably has a backwashing zone. 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.
  • the mass ratio 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 top temperature in the range from 10 to 100 ° C., in particular in the range from 20 to 70 ° C. ° 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- Methyl pyrrolidone (NMP).
  • NMP N- Methyl pyrrolidone
  • 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.
  • Particularly suitable is 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 from 50 to 100% by volume of n-butane, from 0 to 50% by volume of 2-butene and from 0 to 3% by volume of further constituents, such as isobutane, Isobutene, propane, propene and Cs + hydrocarbons.
  • a stream containing the extractant, water, butadiene and in small amounts butene and butane is obtained, which is fed to a distillation column. In this will be recovered overhead or as a side take butadiene.
  • an extractant and water-containing stream is obtained, wherein the composition of the extractant and water-containing stream corresponds to the composition as it is added to the extraction.
  • the extractant and water-containing stream is preferably returned to the extractive distillation.
  • the extraction solution is transferred to a desorption zone, wherein the butadiene is desorbed from the extraction solution.
  • the desorption zone can be designed, for example, in the form of a wash column which has 2 to 30, preferably 5 to 20 theoretical stages and, if appropriate, 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.
  • 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 of 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. Examples
  • 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 pressing pressure and comminuted through a sieve with a mesh size of 0.8 mm.
  • the split was again mixed with 2% by weight graphite and the mixture mixed with a Kilian S100
  • the calcined tablets were ground to a powder.
  • the nozzle was installed in such a way that the spray cone wetted the support body carried in the drum in the upper half of the unrolling section
  • the finely powdered precursor material was introduced into the drum via a powder screw, the point at which the powder was added within the rolling line, but the powder addition was dosed so that a uniform distribution of the powder on the Ob
  • the resulting coated catalyst from the precursor material and the carrier body was dried in a drying oven at 300 ° C. for 3 hours.
  • the Miniplant reactor was a salt bath reactor having a length of 500 cm and an inner diameter of 29.7 mm and a thermowell having an outer diameter of 6 mm.
  • the reaction tube was charged with the catalyst.
  • On a catalyst chair sat a 10 cm long debris consisting of 60 g steatite rings of geometry 7 mm x 4 mm x 7 mm (outer diameter x inner diameter x length).
  • This was followed by 2710 g of an undiluted coated catalyst (bed height 384 cm, 2552 ml bulk volume in the reactor) in the form of hollow cylinders of the dimensions 7 mm ⁇ 4 mm ⁇ 3 mm (outside diameter ⁇ inside diameter ⁇ length).
  • the catalyst bed was followed by an 85 cm long feed consisting of 487 g of steatite rings of geometry 7 mm ⁇ 4 mm ⁇ 7 mm (outer diameter ⁇ inner diameter ⁇ length).
  • the reaction tube was tempered over its entire length with a circulating salt bath at a temperature Tsaizbad of 390 ° C.
  • the reaction starting gas mixture was a mixture of a total of 8% by volume of 1%, cis-2 and trans-2-butenes, 2% by volume of butanes (n- and isobutane), 8.5% by volume of oxygen, 12% by volume of water and 69.5% by volume of nitrogen were used.
  • the load on the reaction tube was 5520 Nl / h of total gas.
  • the salt bath temperature was constant at 390 ° C.
  • the hotspot temperature averaged around 439 ° C and was in the front third of the catalyst bed.
  • the temperature at the end of the bed averaged around 397 ° C.
  • Pressure was measured at the reactor inlet (pi) and at the reactor outlet (P2).
  • the yield of 1,3-butadiene, based on all butenes, and the formation of styrene, anthraquinone and fluorenone in% by volume, based also on all butenes, were determined by gas chromatography.
  • the yield of the component X is calculated as follows
  • Trial 1 As can be seen from Table 1, the formation of the coke precursors styrene, anthraquinone and fluorenone increases markedly above 1.3 bar with increasing pressure. The increase (12.5 to 21, 2%) is disproportionate, since the yield of butadiene only increases moderately (4.6%).

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EP2945923B1 (de) * 2013-01-15 2017-03-15 Basf Se Verfahren zur oxidativen dehydrierung von n-butenen zu butadien
CN106795066A (zh) * 2014-09-26 2017-05-31 巴斯夫欧洲公司 由正丁烯通过氧化脱氢制备1,3‑丁二烯的方法
WO2016143783A1 (ja) * 2015-03-09 2016-09-15 三菱化学株式会社 共役ジエンの製造方法
WO2016177764A1 (de) * 2015-05-06 2016-11-10 Basf Se Verfahren zur herstellung chrom enthaltender katalysatoren für die oxidehydrierung von n-butenen zu butadien unter vermeidung von cr(vi)-intermediaten
CN105175207B (zh) * 2015-10-16 2017-03-22 安徽工业大学 用Bi/Mo/Co/La/Fe五组分复合氧化物催化剂移动床合成1,3‑丁二烯的方法
CN107970945A (zh) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 用于丁烯氧化脱氢制丁二烯的催化剂及其工艺方法
CN107973690A (zh) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 用于丁烯氧化脱氢制丁二烯的催化剂及其方法
CN107970954B (zh) * 2016-10-21 2023-01-31 中国石油化工股份有限公司 用于丁烯氧化脱氢制丁二烯的催化剂及其制备方法
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WO1997037766A1 (fr) * 1996-04-08 1997-10-16 Catalysts & Chemicals Industries Co., Ltd. Catalyseur d'hydrodemetallation d'huile hydrocarbonee et procede d'hydrodemetallation d'huile hydrocarbonee utilisant ce catalyseur
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TW200950880A (en) * 2008-04-09 2009-12-16 Basf Se Coated catalysts comprising a multimetal oxide comprising molybdenum, bismuth and iron

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