公开(公告)号：DE102005051401A1

公开(公告)日：2007-04-26

申请号：DE102005051401

申请日：2005-10-25

Applicant: BASF AG

Inventor： KLANNER CATHARINA ,  DIETERLE MARTIN ,  SCHINDLER GOETZ-PETER ,  CHENG TSUNG-CHIEH ,  MUELLER-ENGEL KLAUS JOACHIM

IPC: C07C57/05 ,  B01J8/02 ,  B01J19/24 ,  C07C5/333 ,  C07C45/28 ,  C07C47/22 ,  C07C57/055

Abstract: Preparation of acrolein/acrylic acid from propane comprises supplying reaction gas mixture input stream A to a reaction zone A; supplying dehydrogenated propane gas stream to obtain a product gas mixture; removing the product mixture stream A; dividing the product gas mixture stream A into component streams (I) and (II); feeding the component stream (II) in a second reaction zone B into an oxidative reactor, in which propylene in stream (II) is oxidized to form a product gas mixture B containing e.g. acrolein/acrylic acid as final product and separating the final product. Preparation of acrolein and/or acrylic acid from propane comprises supplying a reaction gas mixture input stream A (which is produced by merging at least four different gaseous initial streams 1, 2, 3 and 4) to the inlet of the first reaction zone A by at least a catalyst bed; optionally further supplying partially, heterogeneously catalyzed dehydrogenated propane gas stream to the mixture to obtain a product gas mixture containing propane and propylene; removing the obtained product gas mixture stream A from the first reaction zone A by discharge opening; dividing the product gas mixture stream A into two component streams (I) and (II) with identical composition, where the component stream (I) is fed back as gaseous initial stream 1 into the first reaction zone A in a first gas cycle operation and the component stream (II) is optionally led into the first separation zone A, to separate partial or large quantity of different propane and propylene components and to produce a residual product gas mixture stream A1 containing propane and propylene; feeding the component stream (II) or the product gas mixture in a second reaction zone B into at least an oxidative reactor, in which the propylene contained in the component stream (II) or in the product gas mixture stream A1 is subjected to selective heterogeneously catalyzed partial gaseous phase oxidation with molecular oxygen to form a product gas mixture B containing acrolein and/or acrylic acid as final product, optionally unconverted propane and propylene, and surplus molecular oxygen; removing the product gas mixture stream B from the reaction zone B; separating the final product, where the residual gas containing unconverted propane and propylene, and molecular oxygen is fed back as gaseous initial stream 2 in a second gas cycle operation into the reaction zone A (when the gaseous initial streams 2, 3 and 4 and optionally a gaseous stream different from the 1 are merged to a single propelled jet gaseous mixture stream); and subsequently operating the mixture with gaseous propelled jet mixture stream as propelled jet of a jet pump, which comprises a jet nozzle, a mixing path, a diffuser and a suction intake socket; where the direction of the propulsion of the propelled jet by the jet nozzle over a mixing path and the diffuser, points towards the inlet of the first reaction zone A and the suction effect of the suction intake socket, points towards the direction of the discharge opening of the first reaction zone A leading to the product gas mixture stream A and the component stream (I) is sucked through the negative pressure produced in the suction intake socket along with the splitting up of the product gas mixture A into the two component stream, and is transported with simultaneous mixing of propelled jet by the mixing path over the diffuser and the obtained reaction gas mixture input stream A is left into the inlet of the first reaction zone A; the gaseous initial streams 1, 2 and 3 is a propane, the gaseous initial stream 4 is a molecular hydrogen and the gaseous initial stream 3 is a fresh propane; the first gaseous initial stream 2 and 3 and optionally stream 1 and stream 4 are combined in an arbitrary sequence to a single gaseous mixture stream and stream 4 is added to the gaseous initial mixture stream under the formation of the gaseous propelled jet mixture stream.

公开(公告)号：BRPI0416073A

公开(公告)日：2007-01-02

申请号：BRPI0416073

申请日：2004-10-15

Applicant: BASF AG

Inventor： DIETERLE MARTIN ,  PETZOLDT JOCHEN ,  MUELLER-ENGEL KLAUS JOACHIM

IPC: B01J23/00 ,  B01J23/887 ,  B01J23/888 ,  B01J23/94 ,  B01J35/00 ,  B01J38/12 ,  B01J38/14 ,  C07C45/35 ,  C07C47/22

Abstract: The invention relates to the long term operation of a heterogeneously catalysed gas phase partial oxidation of propene in order to form acrolein. The temperature of the solid bed catalyst increases over time, gas phase partial oxidation is interrupted at least once per calendar year, and a gas mixture (G) is guided through the solid bed catalyst having a temperature of between 250 - 550 DEG C, said gas mixture consisting of molecular oxygen, inert gas and, optionally, steam.

公开(公告)号：DE102005017050A1

公开(公告)日：2006-10-19

申请号：DE102005017050

申请日：2005-04-12

Applicant: BASF AG

Inventor： DIETERLE MARTIN ,  MUELLER-ENGEL KLAUS JOACHIM ,  PETZOLDT JOCHEN ,  HAMMON ULRICH

IPC: C07B33/00 ,  C07B35/04 ,  C07B63/00 ,  C07C57/05 ,  C07C57/07

Abstract: Preparing at least one organic target compound (I) by heterogeneously catalyzed gas phase partial oxidation of at least one organic precursor compound with molecular oxygen in at least two oxidation reactor systems comprising catalyst charges and are operated in parallel to obtain at least two product gas streams (II) each comprising (I) and each stemming from one of the at least two oxidation reactor systems and subsequent removal of (I) from (II) to obtain at least one crude target product stream, where the process comprises before, during and/or after the removal, mixing together (II). Preparing at least one organic target compound (I) by heterogeneously catalyzed gas phase partial oxidation of at least one organic precursor compound with molecular oxygen in at least two oxidation reactor systems comprising catalyst charges and are operated in parallel to obtain at least two product gas streams (II) each comprising (I) and each stemming from one of the at least two oxidation reactor systems and subsequent removal of (I) from (II) to obtain at least one crude target product stream, where the process comprises before the removal, mixing together (II); or in the course of the removal, mixing together at least two of any target product-comprising subsequent streams obtained on the route from (II) to the at least one crude target product stream; and/or after the removal from (II), mixing together any crude target product streams obtained in the course of the removal, to form a mixture stream, where at least one of the catalyst charges of the at least two oxidation reactor systems operated in parallel, over which the target compounds comprised in the mixture stream were formed, comprises at least one portion of catalyst over which the heterogeneously catalyzed gas phase partial oxidation has already been carried out longer than over all portions of catalyst of the at least one other catalyst charge. An independent claim is included for an apparatus comprising two oxidation reactor systems which are charged with catalysts that are suitable for the preparation of (I) by heterogeneously catalyzed partial oxidation of an organic precursor compound and at whose outlet is disposed in each case a line for the removal of the product gas stream comprising (I) from the particular oxidation reactor system, which lines are combined with increasing distance from the two oxidation reactor systems to give a product gas line which leads to an apparatus in which the product gas stream can be condensed partly or fully, where the catalyst charge of one of the two oxidation reactor systems comprises at least one portion of catalyst over which more target product has already been generated than over the portions of catalyst of the catalyst charge of the other oxidation reactor system.

公开(公告)号：DE102005013039A1

公开(公告)日：2006-09-21

申请号：DE102005013039

申请日：2005-03-18

Applicant: BASF AG

Inventor： MACHHAMMER OTTO ,  SCHINDLER GOETZ-PETER ,  ADAMI CHRISTOPH ,  HECHLER CLAUS ,  DIETERLE MARTIN

IPC: C07C57/05 ,  C07C5/333 ,  C07C45/33 ,  C07C47/22 ,  C07C57/055 ,  C07C57/07

Abstract: Acrolein and/or acrylic acid is prepared by feeding to a first reaction zone A at least two gaseous, propane-containing feed streams comprising fresh propane, and in reaction zone A, subjecting their propane fed to a heterogeneously catalyzed dehydrogenation to obtain a product gas mixture A comprising propane and propylene. Preparation of acrolein and/or acrylic acid involves feeding to a first reaction zone A at least two gaseous, propane-containing feed streams having fresh propane and in reaction zone A, subjecting their propane fed in this way to a heterogeneously catalyzed dehydrogenation to obtains a product gas mixture A comprising propane and propylene; conducting product gas mixture A out of reaction zone A and in a first separation zone A, removing a portion of the constituents other than propane and propylene in product gas mixture A and using remaining product gas mixture A' comprising propane and propylene; in a second reaction zone B to charge an oxidation reactor and, in the oxidation reaction, subjecting the propylene present in product gas mixture A' to a catalyst gas phase partial oxidation with molecular oxygen to give a product gas mixture B having acrolein or acrylic acid as the target product and also excess molecular oxygen; and conducting product gas mixture b out of reaction zone B and in a second separation zone, removing target product present in product gas mixture B, and of the remaining residual gas having unconverted propane, molecular oxygen and any unconverted propylene as one of the two-propane-containing feed streams into reaction zone A, where this recycling into he reaction zone A along the reaction path of the catalyzed dehydrogenation of propane in reaction zone A is effected such that at the feed point, >=5 mol.% of the propane fed to reaction zone A via the other feed streams has already been converted under dehydrogenating conditions in reaction zone A.

公开(公告)号：DE102005009890A1

公开(公告)日：2006-09-07

申请号：DE102005009890

申请日：2005-03-01

Applicant: BASF AG

Inventor： HEILEK JOERG ,  MUELLER-ENGEL KLAUS JOACHIM ,  ADAMI CHRISTOPH ,  DIETERLE MARTIN

IPC: C07C57/07 ,  C07C45/78 ,  C07C47/22 ,  C07C57/05

Abstract: Separation of a methracrolein from an acrylic acid, comprises crystallizing and separating the acrylic acid, and leaving the methacrolein in a liquid phase of the mother liquor.

公开(公告)号：BRPI0408629A

公开(公告)日：2006-03-28

申请号：BRPI0408629

申请日：2004-03-20

Applicant: BASF AG

Inventor： PETZOLDT JOCHEN ,  DIETERLE MARTIN ,  ARNOLD HEIKO ,  RUPPEL WILHELM ,  MUELLER-ENGEL KLAUS JOACHIM

IPC: C07C51/25 ,  C07C57/05

Abstract: In a process for heterogeneously catalyzed partial gas phase oxidation of propene to acrylic acid, the propene-containing starting reaction gas mixture is oxidized in a first reaction stage using a fixed catalyst bed 1 which consists of a plurality of fixed catalyst bed zones and is accommodated in two successive temperature zones A, B, and the acrolein-containing product gas mixture of the first reaction stage is then oxidized in a second reaction stage using a fixed catalyst bed 2 which consists of a plurality of fixed catalyst bed zones and is accommodated in two successive temperature zones C, D, and the transition from one temperature zone to another temperature zone within one reaction stage does not spatially coincide with a transition from one fixed catalyst bed zone to another fixed catalyst bed zone.

公开(公告)号：DE10351269A1

公开(公告)日：2005-06-02

申请号：DE10351269

申请日：2003-10-31

Applicant: BASF AG

Inventor： DIETERLE MARTIN ,  PETZOLDT JOCHEN ,  MUELLER-ENGEL KLAUS JOACHIM

IPC: C07C51/16 ,  C07C51/25 ,  C07C57/05

Abstract: A heterogeneously catalyzed gas phase partial oxidation of propene to acrylic acid is operated by interrupting gas phase partial oxidation before temperature increase of fixed catalyst bed is permanently 10[deg]C, and at 250-500, preferably 200-450[deg]C, initially conducting a gas mixture consisting of molecular oxygen, inert gas, and optionally steam through intermediate cooler and finally through fixed catalyst bed. The long-term operation of heterogeneously catalyzed gas phase partial oxidation of propene to acrylic acid involves interrupting gas phase partial oxidation before temperature increase of fixed catalyst bed is permanently 10[deg]C, and at 250-500, preferably 200-450[deg]C, initially conducting a gas mixture consisting of molecular oxygen, inert gas, and optionally steam through intermediate cooler and finally through fixed catalyst bed. A starting reaction gas mixture comprising propene, molecular oxygen, and inert gas, and contains the molecular oxygen and propene in a molar ratio of >= 1, is conducted in a first reaction stage, at elevated temperature, over a first fixed catalyst bed whose catalysts are such that their active composition is a multilevel oxide containing molybdenum and/or tungsten, and also bismuth, tellurium, antimony, tin, or copper, in such a way that propene conversion in single pass is >= 93 mol% and the accompanying selectivity of acrolein formation and of acrylic acid by-production taken together are >= 90 mol%, optionally reducing the temperature of the product gas mixture leaving the first reaction stage by direct and/or indirect cooling and optionally adding molecular oxygen and/or inert gas to the product gas mixture, and then conducting the product gas mixture, as starting reaction gas mixture which comprises acrolein, molecular oxygen, and inert gas and contains the molecular oxygen and acrolein in a molar ratio of 0.5, in a second reaction stage, at elevated temperature, over a second fixed catalyst bed whose catalysts are such that their active composition is multilevel oxide containing molybdenum and vanadium, in such a way that acrolein conversion in single pass is >=90 mol% and the selectivity of acrylic acid formation assessed over both reaction stages, based in propene converted, is >=80 mol%, and by, in order to counteract the deactivation of the fixed catalysts bed, independently increasing the temperature of the particular catalyst bed over time.

公开(公告)号：DE10350812A1

公开(公告)日：2005-06-02

申请号：DE10350812

申请日：2003-10-29

Applicant: BASF AG

Inventor： DIETERLE MARTIN ,  PETZOLDT JOCHEN ,  MUELLER-ENGEL KLAUS JOACHIM

IPC: B01J23/00 ,  B01J23/887 ,  B01J23/888 ,  B01J23/94 ,  B01J35/00 ,  B01J38/12 ,  B01J38/14 ,  C07C45/35 ,  C07C47/22 ,  B01J23/84

Abstract: A starting reaction gas mixture which comprises propene, molecular oxygen and inert diluent gases is conducted through fixed catalyst bed. Subsequently, temperature of catalyst bed is increased over time. A gas mixture (G) of molecular oxygen, inert gas and optionally steam, is conducted through the bed at 250-550[deg]C, by long-term operation of heterogeneously catalyzed gas phase partial oxidation of propene to acrolein. A starting reaction gas mixture which comprises propene, molecular oxygen and at least one inert diluent gas is conducted through a fixed catalyst bed at elevated temperature, whose catalysts are such that their active composition is at least one multi metal oxide which contains element which is molybdenum and/or tungsten and at least one of element which is bismuth, tellurium, antimony, tin and copper, so as to counteract the deactivation of fixed catalyst bed. Subsequently, the temperature of the fixed catalyst bed is increased over time. The gas phase partial oxidation is interrupted at least once per calendar year. A gas mixture (G) consisting of molecular oxygen, inert gas and optionally steam, is conducted through the fixed catalyst bed at 250-550[deg]C, by long-term operation of heterogeneously catalyzed gas phase partial oxidation of propene to acrolein.

公开(公告)号：DE10325488A1

公开(公告)日：2004-12-23

申请号：DE10325488

申请日：2003-06-04

Applicant: BASF AG

Inventor： DIETERLE MARTIN ,  HIBST HARTMUT ,  POEPEL WOLFGANG JUERGEN ,  PETZOLDT JOCHEN

IPC: B01J23/00 ,  B01J23/887 ,  B01J23/888 ,  B01J35/00 ,  B01J37/08 ,  C07C51/215 ,  C07C51/235 ,  B01J23/88 ,  C01G31/02 ,  C01G33/00 ,  C01G39/02 ,  C01G41/02

Abstract: Preparation of catalytically active multielement oxide materials containing niobium and/or tungsten, molybdenum, vanadium, and copper, includes thermally treating a dry blend containing ammonium ions and the elemental components of oxide material, other than oxygen at elevated temperature in an atmosphere having low content of molecular oxygen. A portion of ammonium ions in the dry blend is decomposed at >=160[deg]C with liberation of ammonia. Preparation of catalytically active multielement oxide materials containing niobium and/or tungsten, molybdenum, vanadium, and copper, includes thermally treating a dry blend containing ammonium ions and the elemental components of multielement oxide material, other than oxygen at elevated temperature in an atmosphere having a low content of molecular oxygen. A portion of ammonium ions contained in the dry blend is decomposed at >=160[deg]C with liberation of ammonia. Thermal treatment includes heating the dry blend at =10[deg]C/minute to a decomposition temperature (preferably 240-360[deg]C) and holding at this temperature until >=90 mole% of the total amount of ammonia liberated in the entire course of thermal treatment have been liberated; reducing the molecular content in the atmosphere where thermal treatment takes place is reduced to =0.5 vol.% not later than when the intimate dry blend has reached 230[deg]C and maintaining this low oxygen content until >=20 mole% of the total amount of ammonia liberated in the entire course of thermal treatment have been liberated; taking the dry blend at =10[deg]C/minute out of the decomposition temperature and into the calcination temperature of 380-450[deg]C not earlier than when >=70 mole% of the total amount of ammonia liberated in the entire course of thermal treatment have been liberated; and increasing the content of molecular oxygen in the atmosphere to greater than 0.5-4 vol.% not later than when 98 mole% of the total amount of ammonia liberated in the entire course of thermal treatment have been liberated, and calcining the dry blend at this increased oxygen content of atmosphere in the calcination temperature. The molar fraction of molybdenum is 20-80 mole%, based on the total amount of all elements other than oxygen in the multielement oxide material. The molar ratio of molybdenum to vanadium is 15:1 - 1:1. The molar ratio of molybdenum to copper is 30:1 - 1:3. The molar ratio of molybdenum to the total amount of tungsten and niobium is 80:1 - 1:4.

公开(公告)号：DE10313210A1

公开(公告)日：2004-10-07

申请号：DE10313210

申请日：2003-03-25

Applicant: BASF AG

Inventor： PETZOLDT JOCHEN ,  DIETERLE MARTIN ,  ARNOLD HEIKO ,  WILHELM RUPPEL ,  MUELLER-ENGEL KLAUS JOACHIM

IPC: C07C17/35 ,  C07C51/25 ,  C07C47/22 ,  C07C27/14

Abstract: A mixture of propene, molecular oxygen and inert gas, is passed over a fixed catalyst bed having temperature zones (A,B) maintained at 290-380 [deg] C. The fixed catalyst bed has two fixed catalyst bed zones having preset volume-specific activity. The transition from zone A to zone B in fixed catalyst bed do not coincide with transition from one fixed catalyst bed zone to another. The partial oxidation of propene in gaseous phase is performed in presence of heterogeneous catalyst. A reaction gas mixture comprising propene, molecular oxygen and at least one inert gas is passed over a fixed catalyst bed containing at least one multimetal oxide comprising molybdenum, iron and bismuth. The molar ratio of molecular oxygen and propene is = 1. The fixed catalyst bed is arranged in two spatially successive temperature zones (A,B), both maintained at 290-380 [deg] C. The fixed catalyst bed consists of at least two spatially successive fixed catalyst bed zones. The volume-specific activity within one fixed catalyst bed zone is substantially constant and increases sharply in the flow direction of the reaction gas mixture at the transition from one fixed catalyst bed zone to another fixed catalyst bed zone. The temperature zone (A) extends up to a conversion of propene of 40-80 mol%. On single pass of the starting reaction gas mixture through the entire fixed catalyst bed, the propene conversion is >=90 mol% and the selectivity of acrolein formation based on converted propene is >=90 mol %. The sequence in time in which the reaction gas mixture flows through the temperature zones (A,B) corresponds to the alphabetic sequence of the temperature zones. The hourly space velocity of the propene contained in the reaction gas mixture on the fixed catalyst bed is >= 90 I(STP) of propene/I of fixed bed catalyst.h. The difference (TmaxA-TmaxB) between the highest temperature (TmaxA) of reaction gas mixture in zone A, and the highest temperature (TmaxB) of reaction gas mixture in zone B, is >=0 [deg] C. The transition from temperature zone A to temperature zone B in the fixed catalyst bed do not coincide with a transition from one fixed catalyst bed zone to another fixed catalyst bed zone.