WO2014086965A1 - Schalenkatalysator zur oxidativen dehydrierung von n-butenen zu butadien - Google Patents
Schalenkatalysator zur oxidativen dehydrierung von n-butenen zu butadien Download PDFInfo
- Publication number
- WO2014086965A1 WO2014086965A1 PCT/EP2013/075777 EP2013075777W WO2014086965A1 WO 2014086965 A1 WO2014086965 A1 WO 2014086965A1 EP 2013075777 W EP2013075777 W EP 2013075777W WO 2014086965 A1 WO2014086965 A1 WO 2014086965A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- multimetal oxide
- butenes
- carrier body
- butadiene
- shell
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 96
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims description 70
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims description 28
- 239000002245 particle Substances 0.000 claims abstract description 41
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 26
- 239000011733 molybdenum Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000012702 metal oxide precursor Substances 0.000 claims abstract 4
- 239000007789 gas Substances 0.000 claims description 117
- 239000000203 mixture Substances 0.000 claims description 77
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 35
- 239000001301 oxygen Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 29
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- 239000002243 precursor Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
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- 238000002360 preparation method Methods 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
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- 229910052792 caesium Inorganic materials 0.000 claims description 6
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- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 10
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- 239000007858 starting material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 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
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- B01J23/74—Iron group metals
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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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/74—Iron group metals
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
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- 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
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- 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
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- 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
- C07C2523/28—Molybdenum
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- 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
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- 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
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- 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
Definitions
- the invention relates to 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 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). 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.
- 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,
- 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 having the composition Moi 2 Bi 5 Co 2 .5 Ni 2 .5 Feo, 4 ao, 35Bo, 2Ko, 8Si24 is in the form of tablets having a diameter of 5 mm and a height of 4 mm in the oxidative dehydrogenation of n-butenes to butadiene used.
- a problem is the often low mechanical stability of the shell of active material of the shell catalyst. Due to the mechanical stress of the shell catalyst during filling of the reactor with the catalyst particles and during operation of the reactor loses the shell catalyst active material in the form of finely divided abrasion. The finely divided abrasion of the active mass can accumulate at certain points in the reactor. At these points then there is a very high local concentration of active material, with the result that the heat of reaction is no longer sufficiently dissipated and there may be an uncontrolled acceleration of the reaction. The uncontrolled conversion reduces the butadiene selectivity. WEI In addition, overheating can cause damage to the reactor or other parts of the system.
- An accumulation of abrasion of the active mass in the catalyst bed can also lead to increased formation of coke deposits at these points. Coking can lead to an increase in the pressure drop over the catalyst bed. Due to the described adverse effects of abrasion interruption of the operation may be necessary, which adversely affects the economics of the process.
- the object of the invention is to provide a shell catalyst for the oxidative dehydrogenation of n-butenes to butadiene, which has improved mechanical stability.
- coated catalysts according to the invention whose shell is composed of multimetal oxide particles having a d 50 value of from 6 to 13 ⁇ m, have a particularly low attrition.
- the multimetal oxide particles have a d 50 value of 8 to 13 ⁇ m, more preferably of 9 to 12 ⁇ m.
- the dso value is defined according to ISO 13320 as the median value of the particle diameter on a volumetric basis. This means that 50% by volume of the particles have a smaller diameter and 50% by volume have a larger diameter than the dso value.
- the particle diameter distributions and the resulting dso value are determined by laser diffraction according to ISO 13320.
- the particle diameter distribution can be determined by passing the finely divided powder through a dispersing chute into a dry disperser Sympatec RODOS (Sympatec GmbH, System-Particle Technology, Clausthal-Zellerfeld), then dry-dispersed with compressed air and blown in a free jet into a measuring cell ,
- the volume-related particle diameter distribution is determined according to ISO 13320 with a Malvern Mastersizer S laser diffraction spectrometer (Malvern Instruments, Worcetshire, United Kingdom).
- the attrition of the coated catalyst according to the invention can be determined in a drop test.
- a coated and thermally post-treated coated catalyst are filled within 30 seconds from the top into a vertical, 350 cm long tube reactor.
- the shaped catalyst bodies and the finely divided flakes of the active composition are removed, separated from each other and weighed.
- the mass of the flakes is related to the mass of the total amount of active material applied to the carrier body.
- the abrasion of the coated catalyst according to the invention is ⁇ 15%, preferably ⁇ 1 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.
- 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.
- the catalytically active, molybdenum-containing 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;
- 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
- Suitable multimetal oxides and their preparation are further described in US 4,423,281 (Moi2BiNi 8 Pbo, 5 Cr 3 Ko, 20x and Moi2BibNi 7 Al 3 Cro, 5Ko, 50x), US 4,336,409 (Moi2BiNi 6 Cd2Cr 3 Po, 5 Ox), DE-A 26 00 128 (Moi2BiNi 0 , 5Cr 3 Po, 5 Mg7, 5 Ko, iOx + Si0 2 ) and DE-A 24 40 329 (Moi2BiCo4,5Ni 2 , 5Cr 3 Po, 5 Ko, iOx).
- 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 sa.sup.-1, more preferably 0.4.ltoreq.a.95.
- the value for the variable b is preferably in the range 1 ⁇ bs 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 + ds 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 expediently> 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 has a carrier body (a) and a shell (b) containing the catalytically active, molybdenum and at least one further metal-containing multimetal oxide.
- the shell (b) is preferably produced without pore-forming agents.
- the use of pore formers can improve the transport properties in the individual catalyst grain.
- the abrasion resistance of a catalyst can be greatly reduced by the use of pore formers. Attrition of the catalyst may accumulate in the reactor bed resulting in uncontrolled reactions and / or a large increase in pressure loss.
- the carrier bodies (a) may be regularly or irregularly shaped, with regularly shaped carrier bodies having a marked surface roughness, e.g. Balls, cylinders or hollow cylinders are preferred. Their longest extent is usually 1 to 10 mm.
- 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 .-%).
- An increased surface roughness of the carrier body usually causes an increased adhesive strength of the applied shell and can be achieved for example by a so-called chippings support.
- the surface roughness RZ of the carrier body (a) is in the range of 30 to 100 ⁇ m, preferably 50 to 70 ⁇ m (determined according to DIN 4768, sheet 1 with a "Hommel tester for DIN-ISO surface measured quantities" from Hommelwerke.) CeramTec from Steatit C 220 are surface roughened carrier bodies.
- the wall thickness is usually between 1 and 4 mm
- annular carrier bodies preferably have a length of 2 to 2 mm s 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm.
- Particularly suitable are rings of geometry 7 mm x 3 mm x 4 mm (outer diameter x length x inner diameter) as a carrier body.
- Preferred carrier bodies are 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 0.2 to 1, 5 times the outer diameter.
- the hollow cylindrical carrier body (a) the dimensions outside diameter x length x inside diameter (4 to 10 mm) x (2 to 8 mm) x (1 to 10 mm) on.
- the carrier body (a) particularly preferably has the dimensions outer diameter x length x inner diameter (4 to 8 mm) x (2 to 5 mm) x (1 to 5 mm).
- the layer thickness D of the shell (b) of a molybdenum and at least one further metal-containing multimetal oxide composition is generally from 50 to 1000 ⁇ m. Preference is given to 50 to 800 ⁇ m, particularly preferably 50 to 600 ⁇ m, and very particularly preferably 80 to 500 ⁇ m.
- the shell catalyst is prepared by applying to the carrier body by means of a binder by means of a layer containing the molybdenum and at least one further metal-containing multimetal, dries the coated carrier body and thermally treated.
- the multimetal oxide particles applied to the carrier body with a binder have a d 50 value of 6 to 13 ⁇ m.
- the invention also provides a process for the preparation of a shell catalyst comprising
- a first step (i) the molybdenum and at least one further metal-containing multimetal oxide precursor composition is prepared.
- suitable finely divided multimetal oxide precursor compositions starting from known starting compounds of the elemental constituents of the desired multimetal oxide precursor 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. Come next to the oxides therefore, as starting compounds in particular halides, nitrates, formates, oxalates, acetates, carbonates or hydroxides into consideration.
- 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 35 ° C and 80 ° C.
- 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 preferably takes place by spray drying.
- the suspension is sprayed at elevated temperature with a spray head, the temperature of which 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% by weight, preferably less than 15% by weight and more preferably less than 12% by weight.
- molded articles are produced from the multimetal oxide precursor composition.
- the spray powder is transferred in a further step in a shaped body (Katalysatorvortechnikrformève).
- Suitable shaping aids 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, in many cases ⁇ 4% by weight of shaping aid added medium. Usually, the aforementioned additional amount is> 0.5 wt .-%.
- Possible slip aids are described for example in DE102007005606. Slip aid preferred according to the invention is graphite.
- the shaped body of the multimetal oxide precursor composition is calcined to a multimetal oxide composition.
- the calcination of the catalyst precursor molding is usually carried out at temperatures exceeding 350 ° C. Normally, however, the thermal treatment does not exceed the temperature of 650 ° C.
- the temperature of 600 ° C. preferably the temperature of 550 ° C. and particularly preferably the temperature of 500 ° C.
- the thermal treatment can also be divided into several sections in their time sequence.
- a thermal treatment at a temperature of 150 to 350 ° C, preferably 220 to 280 ° C, and then a thermal treatment at a temperature of 400 to 600 ° C, preferably 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 (also referred to below as the decomposition phase) of the catalyst precursor molding can be carried out both under inert gas and under an oxidative atmosphere such as air (mixture of inert gas and oxygen) and under reducing atmosphere (eg mixture of inert gas, NH 3, CO and / or H2 or methane).
- the thermal treatment can also be carried out under vacuum.
- the thermal treatment of the catalyst precursor moldings can be carried out in a wide variety of furnace types, such as, for example, heatable circulating air chambers, tray ovens, rotary kilns, belt calciners or shaft kilns.
- 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 calcined shaped body of multimetal oxide is ground to multimetal oxide particles having a d 50 value of 6 to 13 ⁇ m. Any suitable mill can be used. The grinding is preferably carried out to this particle size in classifier mills.
- Crushing tool is a rotor, which is occupied at the outer edge with impact plates.
- the rotor is normally horizontal for mills with a static sifter and vertically for mills with a dynamic sifter. It turns at peripheral speeds of up to 120 m / s.
- the product to be ground is supplied to the rotor centrally, crushed by the impact elements and then bounces on a grinding path, which concentrically surrounds the rotor, with a further comminution takes place. After multiple exposure, the gas stream drawn through the mill transports the particles into the viewing zone.
- this consists of an aperture located behind the rotor with a downstream impeller.
- a gas vortex forms in front of the diaphragm.
- the centrifugal force and the drag force of the gas act on the circularly rotating particles.
- the drag force is higher and they go back into the grinding zone, with finer particles, the drag force is greater.
- the latter leave the mill with the gas flow through the aperture as regrind.
- the sighting does not take place in a gas vortex but in a classifier wheel. This usually consists of a rotating wheel, in which there are gaps between webs.
- the particles transported by the grinding gas between the lamellae are accelerated to a circular path and separated by centrifugal and dragging forces.
- the deflector wheel allows a much sharper separation than the static classifier.
- the average fineness and the steepness of the particle size distribution are essentially influenced by the following parameters: peripheral speed (rotational speed) of the grinding rotor, number and type of impact elements, type of grinding path, centrifugal acceleration (speed) of the classifier / diaphragm diameter, gas flow rate, product throughput.
- the carrier body is coated with the multimetal oxide particles.
- Suitable carrier materials for shell-type catalysts according to the invention are porous or preferably nonporous aluminas, silica, 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, which means that they have no catalytic activity with respect to the reaction of the organic constituents contained in the starting material gas under the reaction conditions of the oxidative dehydrogenation.
- 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 support bodies are 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.
- 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 processes 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 or to the surface of the first layer by means 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 at 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.
- Particularly preferred 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 above-described process is preferably repeated several times, i. 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 in a preferably inclined (tilt angle is usually 30 to 90 °) rotating rotary container (e.g., turntable or coating pan).
- 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 mass powder, which compacts by the rolling movement 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, where it is moistened in a controlled manner in order to be able to take up a further layer of finely divided mass in the course of further movement. Interim drying is generally not necessary.
- 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.
- a particular advantage of the embodiment of the method described above is that in one operation shell catalysts can be produced with shells consisting of two or more different masses in a layered manner.
- the method causes both a fully satisfactory adhesion of the successive layers to each other, as well as the base layer on the surface of the carrier body. This also applies in the case of annular carrier bodies.
- the coated carrier body is thermally treated.
- 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.
- the time to remove the primer may be several hours.
- the catalyst is generally heated at said temperature for between 0.5 and 24 hours to remove the coupling agent. Preferred is the time 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 the use of the coated catalysts according to the invention in a process for the oxidative dehydrogenation of 1-butene and / or 2-butenes to butadiene.
- the catalysts according to the invention are notable for high activity, but in particular also for high selectivity with respect to the formation of 1,3-butadiene from 1-butene and 2-butene, as well as high abrasion resistance.
- 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. is brought into contact with a shell catalyst according to the invention arranged in a fixed catalyst bed.
- the temperature data refer to the temperature of the heat exchange medium at the inlet for the heat exchange medium at the reactor.
- the reaction temperature of the oxydehydrogenation is generally controlled by a heat exchange medium located around the reaction tubes.
- Suitable liquid heat exchange agents include, for example, melts of salts such as potassium nitrate, potassium nitrite, sodium nitrite and / or sodium nitrate and melts of metals such as sodium, mercury and alloys of various metals. 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. Due to the exothermic nature of the reactions taking place, 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 can also be determined by the ratio of the catalyst layer or the flow of mixed gas are regulated.
- 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 tubular reactor or in the tubular 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 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. 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.
- 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 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. Furthermore, in the starting oxydehydrogenation gas, any impurities may be present in a range in which the effect of the present invention is not inhibited.
- any impurities may be present in a range in which the effect of the present invention is not inhibited.
- butadiene from n-butenes (1-butene and cis- / trans-2-butene
- impurities saturated and unsaturated, branched and unbranched hydrocarbons such as e.g.
- 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.
- 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 further water (as water vapor) may also be contained together with the mixed gas of raw gas and the gas containing molecular oxygen.
- Nitrogen is used 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.
- steam it is preferable to introduce a content 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.
- 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 1 , preferably 800-4000 hr 1 and even more preferably 1200-3500 r 1 .
- the load of the catalyst to butenes (expressed in gButene (gKatai ator yS * hour) generally is in the stable operation -5.0 0.1 hr 1, preferably 0.2-3.0 h -1, and more preferably 0, 25-1, 0 hl -1 Volume and mass of the catalyst refer to the complete catalyst consisting of carrier and active mass
- the product gas stream leaving the oxidative dehydrogenation generally contains unreacted n-butane and isobutane, 2-butene and steam.
- the product gas stream leaving the oxidative dehydrogenation 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.
- 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
- 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. 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.
- heat exchangers 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.
- the two or more heat exchangers provided may be arranged in parallel.
- the product gas is supplied to one or more, but not all, heat exchangers, and after a certain period of operation, these heat exchangers can be detached from 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, an aromatic hydrocarbon compound can be used. and an alkaline aqueous solvent such as 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.
- the peroxides are very unstable compounds that can spontaneously decompose at temperatures between 85 and 110 ° C.
- a particular danger is the high impact sensitivity of the peroxides, which explode with the explosiveness of an explosive.
- the danger of polymer formation is given especially in the distillative separation of butadiene and can there lead to deposits of polymers (formation of so-called "popcorn") in the columns.
- 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.
- a gas stream is obtained in which n-butane, 1-butene, 2-butenes, butadiene, optionally oxygen, hydrogen, water vapor, remain in small amounts of methane, ethane, ethene, propane and propene, isobutane, carbon oxides and inert gases , 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, wherein at least one condensate stream comprising water condenses out and a gas stream comprising n-butane, 1-butene, 2-butenes, butylene tadiene, 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.
- 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, if required, be used at least partly in hydrogenation or else supplied to other utilization, for example for the production of 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, which are easily sieved Hydrocarbons (methane, ethane, ethene, propane, propene) and inert gas such as optionally nitrogen in an absorption / desorption cycle separated by means of a high-boiling absorbent, whereby 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, 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, for example, tray columns with bells, centrifugal and / or sieve bottom, columns with structured packings, for example sheet metal packings having a specific surface area of 100 to 1000 m 2 / m 3 such as Mellapak® 250 Y, and packed columns. However, there are also trickle and spray towers, graphite block absorbers, surface absorbers such as thick film and thin-layer absorbers and rotary columns, dishwashers, cross-flow scrubbers and rotary scrubbers into consideration.
- an absorption column is supplied in the lower region of the butadiene, butene, butane, and / or nitrogen and optionally oxygen, hydrogen and / or carbon dioxide-containing material stream. In the upper region of the absorption column, the solvent and optionally water-containing material stream is abandoned.
- Inert absorbent used in the absorption stage are generally high-boiling nonpolar 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, in which 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.
- the C4 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, 0 to 10% by volume of 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 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 completely or partially 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 is brought into contact with an extractant, preferably an N-methylpyrrolidone (NMP) / water mixture, in an extraction zone.
- NMP 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 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 of 100 to 250 ° C, in particular at a temperature in the range of 1 10 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.
- 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 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.
- an extractant and water-containing material stream is obtained, the composition of the extractant and water-containing material stream corresponding 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 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.
- 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 solution B was pumped to solution A by means of a peristaltic pump within 15 min. During the addition and then by means of an intensive mixer (Ultra-Turrax) was stirred. After completion of the addition, stirring was continued for a further 5 minutes.
- an intensive mixer Ultra-Turrax
- the suspension obtained was spray-dried in a spray tower from NIRO (spray head No. FOA1, speed 25000 rpm) for a period of 1.5 h.
- 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 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 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:
- the catalyst of the calculated stoichiometry Mo12Co7Fe3Bio.6K008Cro.5Ox was obtained.
- the calcined rings were ground to a powder.
- an ultra-centrifugal mill (Retsch ZM200) was used.
- the device has a horizontal rotor plate, on whose outer edge a certain number of impact elements is mounted vertically upwards. The impact elements are all at the same distance from each other. Outside the rotor is a ring screen attached. Rotor and sieve are located in a grinding chamber housing, which is closed on all sides. Only above the rotor center is an opening.
- the rotor is brought into a fast rotary movement and the comminuted material is applied to the center of the rotor from above.
- the shredded material is ground by the impact elements and passes through the ring sieve.
- the final fineness of the material to be comminuted is determined by the type of rotor, the rotor speed, the ring sieve and the fracture behavior of the material to be comminuted.
- the particle diameter distributions and the particle diameter döo taken from these were determined by laser diffraction.
- the respective finely divided powder was passed through a dispersion trough into the dry disperser Sympatec RODOS (Sympatec GmbH, System Particle Technology, Clausthal-Zellerfeld, DE), where it was dry-dispersed with compressed air and blown into the measuring cell in the free jet.
- the volume-related particle diameter distribution was then determined in accordance with ISO 13320 using the Malvern Mastersizer S laser diffraction spectrometer (Malvern Instruments, Worcetshire, United Kingdom).
- the degree of dispersion of the dry powder during the measurement was determined by the applied dispersion pressure of the compressed air used as propellant gas. The total pressure was 1, 2 bar.
- FIG. 1 shows the integral plot of the particle size distribution in volume percent.
- FIG. 2 shows the differential plot of the particle size distribution in particle percent.
- Two batches of carrier bodies (steatite rings) measuring 7 ⁇ 3 ⁇ 4 mm (outer diameter ⁇ height ⁇ inner diameter) were each coated with 20% by weight of the active compositions A and B in order to obtain catalysts 1 and 2.
- two batches of carrier bodies (steatite rings) having dimensions of 5 ⁇ 3 ⁇ 2 mm (outer diameter ⁇ height ⁇ inner diameter) were coated with in each case 10% by weight of the active compositions B and C in order to obtain catalysts 3 and 4.
- the drum was rotated (25 rpm).
- Liquid binder mixture of glycerol: water 10: 1
- 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 fine powdery active material was introduced into the drum via a powder screw, with the point of powder addition being within the rolling gap but below the spray cone.
- the active composition addition was metered so that a uniform distribution of the powder was formed on the surface.
- the resulting coated catalysts of active composition and the support body were dried in a drying oven at 300 ° C for 3 hours.
- the stability of a shell catalyst can be characterized by attrition in a drop test. For this purpose, about 50 grams of the catalysts 1-4 were filled within 30 seconds from the top into a vertical, 350 cm long tube reactor. The catalyst bodies and the abrasion were removed and separated and weighed. The mass of the abrasion was related to the mass of the applied active mass.
- Table 2 shows the abrasion of active composition in percent, based on the mass of the applied to the carrier body active composition, for the three active materials A, B and C on the catalysts 1 -4: Table 2
- the abrasion is lowest for a dso value of greater than 6 ⁇ and less than 13 ⁇ .
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CN201380063783.1A CN104853842A (zh) | 2012-12-06 | 2013-12-06 | 用于将正丁烯氧化脱氢成丁二烯的壳型催化剂 |
EP13801580.5A EP2928602A1 (de) | 2012-12-06 | 2013-12-06 | Schalenkatalysator zur oxidativen dehydrierung von n-butenen zu butadien |
EA201591088A EA201591088A1 (ru) | 2012-12-06 | 2013-12-06 | Оболочечный катализатор для окислительного дегидрирования н-бутенов в бутадиен |
JP2015546027A JP2016500334A (ja) | 2012-12-06 | 2013-12-06 | n−ブテン類からブタジエンへの酸化的脱水素化のためのシェル触媒 |
KR1020157014754A KR20150093164A (ko) | 2012-12-06 | 2013-12-06 | n-부텐의 부타디엔으로의 산화성 탈수소화를 위한 쉘 촉매 |
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JP (1) | JP2016500334A (de) |
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EP2945923B1 (de) * | 2013-01-15 | 2017-03-15 | Basf Se | Verfahren zur oxidativen dehydrierung von n-butenen zu butadien |
JP2017056398A (ja) * | 2015-09-15 | 2017-03-23 | 旭化成株式会社 | 金属酸化物触媒、その製造方法、及びブタジエンの製造方法 |
KR101742860B1 (ko) * | 2015-01-02 | 2017-06-01 | 주식회사 엘지화학 | 부타디엔 제조용 복합산화물 촉매 및 이의 제조방법 |
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DE4442346A1 (de) * | 1994-11-29 | 1996-05-30 | Basf Ag | Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse |
WO2009124945A2 (de) * | 2008-04-09 | 2009-10-15 | Basf Se | Schalenkatalysatoren enthaltend ein molybdän, bismut und eisen enthaltendes multimetalloxid |
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KR101086731B1 (ko) * | 2008-10-17 | 2011-11-25 | 금호석유화학 주식회사 | 1-부텐의 산화/탈수소화 반응에서 1,3-부타디엔 제조용 비스무스 몰리브덴 철 복합 산화물 촉매 및 제조방법 |
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- 2013-12-06 KR KR1020157014754A patent/KR20150093164A/ko not_active Application Discontinuation
- 2013-12-06 WO PCT/EP2013/075777 patent/WO2014086965A1/de active Application Filing
- 2013-12-06 EP EP13801580.5A patent/EP2928602A1/de not_active Withdrawn
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DE4442346A1 (de) * | 1994-11-29 | 1996-05-30 | Basf Ag | Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse |
WO2009124945A2 (de) * | 2008-04-09 | 2009-10-15 | Basf Se | Schalenkatalysatoren enthaltend ein molybdän, bismut und eisen enthaltendes multimetalloxid |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2945923B1 (de) * | 2013-01-15 | 2017-03-15 | Basf Se | Verfahren zur oxidativen dehydrierung von n-butenen zu butadien |
KR101742860B1 (ko) * | 2015-01-02 | 2017-06-01 | 주식회사 엘지화학 | 부타디엔 제조용 복합산화물 촉매 및 이의 제조방법 |
JP2017056398A (ja) * | 2015-09-15 | 2017-03-23 | 旭化成株式会社 | 金属酸化物触媒、その製造方法、及びブタジエンの製造方法 |
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CN104853842A (zh) | 2015-08-19 |
EP2928602A1 (de) | 2015-10-14 |
EA201591088A1 (ru) | 2015-12-30 |
KR20150093164A (ko) | 2015-08-17 |
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