US20020085975A1 - Method to equalize heat distribution in reactor tube - Google Patents
Method to equalize heat distribution in reactor tube Download PDFInfo
- Publication number
- US20020085975A1 US20020085975A1 US09/754,793 US75479301A US2002085975A1 US 20020085975 A1 US20020085975 A1 US 20020085975A1 US 75479301 A US75479301 A US 75479301A US 2002085975 A1 US2002085975 A1 US 2002085975A1
- Authority
- US
- United States
- Prior art keywords
- tube
- catalytic
- monolith
- center
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000009826 distribution Methods 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005336 cracking Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/2485—Monolithic reactors
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2425—Tubular reactors in parallel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
- B01J2208/023—Details
- B01J2208/024—Particulate material
- B01J2208/025—Two or more types of catalyst
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B01J35/56—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
Definitions
- the invention is to a process to equalize heat distribution in reactor tubes containing catalyst.
- Isothermic tube reactors loaded with catalyst are limited in performance by heat transfer in the catalyst-loaded tubes.
- heat is removed from the center of the tube, making the tube wall temperature substantially higher than the temperature at the tube center.
- the heat of the reaction causes the catalyst in the center zone of the catalyst bed to be substantially higher in temperature than the outside regions of the catalyst bed near the tube wall.
- the temperature differential may have various adverse affects.
- the cool portion of a load may remain too cool for effective catalytic processing and the hot portion of a load may have a shorter than anticipated life center. In all instances the processing efficiency is sacrificed.
- catalytic monoliths allow heat to be directed in the desired direction(s), reducing heat gradients and increasing efficiency and catalyst performance.
- a method for equalizing heat distribution across a catalyst in a tube reactor comprising loading each tube of the tube reactor with one or more catalytic monoliths.
- monolith catalysts catalyst with ceramic supports having uni- or multi-directional channels.
- One or more catalytically reactive metals may be impregnated on the support, or the support material itself may be catalytically reactive.
- Monolith catalysts have an advantage of being able to be formed to a shape which approximates the shape of the container.
- monolith catalysts for tube reactors may be quite long (inches to feet in length) and cylindrical in shape, typically of a diameter just smaller than the inner diameter of the tube in which the monolith catalyst will be placed.
- Uni- or multi-directional channels may be molded into the monoliths to direct the flow of feed as desired. In this manner, each individual channel is equivalent in surface area to many loose catalyst particles.
- the surfaces of the channels are impregnated with catalytically reactive metals or metal compounds, making each channel effective as a catalyst having a surface area equal to the surface area of the channel.
- the monolith may be made of a catalytically reactive material.
- the heat distribution across the catalyst in a tube reactor is equalized by directing the heat as desired down the channels of the monolith catalysts loaded in the tubes of tube reactors. Heat may be directed inwardly, to equalize the temperature profile across the tube of an endothermic reactor, or outwardly, to equalize the temperature profile across the tubes of an exothermic reactor.
- Monolith catalysts used as described have the additional advantage of reducing pressure drop through the catalyst bed.
- Tubular isothermal reactors have inherently high pressure drops in comparison to radial flow adiabatic reactors. This places the tubular reactors at an activity and selectivity disadvantage.
- the monolith catalysts thus described are useful to control the tubular temperature profile of other endothermic reactions, such as dehydrogenation processes and olefin cracking processes.
- the monolith catalysts may also be modified such that the channels direct heat away from the center of the reactor tubes, thus making them useful for exothermic reactions, such as the vapor phase production of epoxides and other oxygenation processes, and hydrocracking processes.
Abstract
There is provided a method for equalizing heat distribution across a catalyst in a tube reactor comprising loading each tube of the tube reactor with one or more catalytic monoliths.
Description
- The invention is to a process to equalize heat distribution in reactor tubes containing catalyst.
- Isothermic tube reactors loaded with catalyst are limited in performance by heat transfer in the catalyst-loaded tubes. For endothermic reactions, heat is removed from the center of the tube, making the tube wall temperature substantially higher than the temperature at the tube center. For exothermic reactions, the heat of the reaction causes the catalyst in the center zone of the catalyst bed to be substantially higher in temperature than the outside regions of the catalyst bed near the tube wall. The temperature differential may have various adverse affects. The cool portion of a load may remain too cool for effective catalytic processing and the hot portion of a load may have a shorter than anticipated life center. In all instances the processing efficiency is sacrificed.
- Heat transfer problems make isothermic reactors less efficient and less commercially attractive than adiabatic systems. This is especially true in endothermic systems, where high tube wall temperatures are needed in isothermic reactors to get sufficient heat to the center of the tubes, resulting in high temperature gradients and non-optimal performance.
- Use of catalytic monoliths allow heat to be directed in the desired direction(s), reducing heat gradients and increasing efficiency and catalyst performance. There is provided a method for equalizing heat distribution across a catalyst in a tube reactor comprising loading each tube of the tube reactor with one or more catalytic monoliths.
- By “monolith catalysts” is meant catalyst with ceramic supports having uni- or multi-directional channels. One or more catalytically reactive metals may be impregnated on the support, or the support material itself may be catalytically reactive. Monolith catalysts have an advantage of being able to be formed to a shape which approximates the shape of the container. Thus monolith catalysts for tube reactors may be quite long (inches to feet in length) and cylindrical in shape, typically of a diameter just smaller than the inner diameter of the tube in which the monolith catalyst will be placed. Uni- or multi-directional channels may be molded into the monoliths to direct the flow of feed as desired. In this manner, each individual channel is equivalent in surface area to many loose catalyst particles.
- The surfaces of the channels are impregnated with catalytically reactive metals or metal compounds, making each channel effective as a catalyst having a surface area equal to the surface area of the channel. Or alternatively, the monolith may be made of a catalytically reactive material.
- The heat distribution across the catalyst in a tube reactor is equalized by directing the heat as desired down the channels of the monolith catalysts loaded in the tubes of tube reactors. Heat may be directed inwardly, to equalize the temperature profile across the tube of an endothermic reactor, or outwardly, to equalize the temperature profile across the tubes of an exothermic reactor.
- Monolith catalysts used as described have the additional advantage of reducing pressure drop through the catalyst bed.
- A particular use of the process occurs in commercial isothermal reactors for styrene production by dehydrogenation of ethyl benzene, an endothermic reaction. These type reactors are plagued by three main problems:
- Low liquid hourly space velocities are required for the reaction, making large diameter tubes necessary. Since the styrene reaction is endothermic heat must be added and the larger tubes increase the temperature differentials from the outside of the tube to the center of the catalyst bed, resulting in poor catalyst performance. Further, as the tube wall temperatures are increased to try and drive heat to the center of the load, the temperatures at the tube walls may reach a level in which cracking of the ethyl benzene and styrene may occur, resulting in undesirable by-products.
- Tubular isothermal reactors have inherently high pressure drops in comparison to radial flow adiabatic reactors. This places the tubular reactors at an activity and selectivity disadvantage.
- One (1) mole of feed (ethyl benzene) becomes two (2) moles of product (styrene+hydrogen), exasperating the above described problems.
- Use of monolith catalysts allow heat to be directed to the center of the catalyst bed in each tube, reducing tube wall temperatures and cracking of the feed and product to undesirable by—products. Also, the pressure drop achieved favors the styrene reaction.
- The monolith catalysts thus described are useful to control the tubular temperature profile of other endothermic reactions, such as dehydrogenation processes and olefin cracking processes. The monolith catalysts may also be modified such that the channels direct heat away from the center of the reactor tubes, thus making them useful for exothermic reactions, such as the vapor phase production of epoxides and other oxygenation processes, and hydrocracking processes.
- It will be apparent to one of ordinary skill in the art that many changes and modifications may be made to the invention without departing from its spirit or scope as set forth herein.
Claims (5)
1. A method for equalizing heat distribution across a catalyst in a tube reactor comprising loading each tube of the tube reactor with one or more catalytic monoliths.
2. A method according to claim 1 wherein said catalytic monolith is a ceramic monolith support impregnated with one or more catalytically reactive metals.
3. A method according to claim 1 wherein said catalytic monolith is an iron oxide useful in the catalytic dehydrogenation of ethyl benzene to styrene; and wherein flow paths in the catalytic monoliths are oriented to direct heat towards a center of each tube.
4. A method according to claim 2 wherein said catalytically reactive metal is selected from the group nickel, cobalt, and molybdenum; wherein said catalytic monolith is useful in the dehydrogenation of hydrocarbons; and wherein flow paths in the catalytic monoliths are oriented to direct heat towards a center of each tube.
5. A method according to claim 2 wherein said catalytically reactive metal is silver; wherein said catalytic monolith is useful in the vapor phase production of epoxides; and wherein flow paths in the catalytic monoliths are oriented to direct heat away from a center of each tube.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/754,793 US20020085975A1 (en) | 2001-01-04 | 2001-01-04 | Method to equalize heat distribution in reactor tube |
| JP2001393138A JP2002263476A (en) | 2001-01-04 | 2001-12-26 | Method of equalizing heat distribution in reactor tube |
| DE10200050A DE10200050A1 (en) | 2001-01-04 | 2002-01-02 | Process for equalizing the heat distribution in a reactor tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/754,793 US20020085975A1 (en) | 2001-01-04 | 2001-01-04 | Method to equalize heat distribution in reactor tube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20020085975A1 true US20020085975A1 (en) | 2002-07-04 |
Family
ID=25036361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/754,793 Abandoned US20020085975A1 (en) | 2001-01-04 | 2001-01-04 | Method to equalize heat distribution in reactor tube |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20020085975A1 (en) |
| JP (1) | JP2002263476A (en) |
| DE (1) | DE10200050A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3573746A4 (en) * | 2017-01-24 | 2020-10-21 | BASF Corporation | Monolithic catalysts for epoxidation |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA3004298C (en) * | 2015-11-04 | 2020-04-28 | Exxonmobil Chemical Patents Inc. | Fired tube conversion system and process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912077A (en) * | 1988-07-15 | 1990-03-27 | Corning Incorporated | Catalytically active materials and method for their preparation |
| US5217936A (en) * | 1989-10-16 | 1993-06-08 | Haldor Topsoe A/S | Catalyst for preparing aldehyde |
| US6005143A (en) * | 1998-08-07 | 1999-12-21 | Air Products And Chemicals, Inc. | Use of a monolith catalyst for the hydrogenation of dinitrotoluene to toluenediamine |
| US6166283A (en) * | 1998-09-03 | 2000-12-26 | The Dow Chemical Company | On-line synthesis and regenerating of a catalyst used in autothermal oxidation |
| US6623707B1 (en) * | 2000-06-19 | 2003-09-23 | Corning Incorporated | Monolithic catalyst dehydrogenation reactor |
-
2001
- 2001-01-04 US US09/754,793 patent/US20020085975A1/en not_active Abandoned
- 2001-12-26 JP JP2001393138A patent/JP2002263476A/en active Pending
-
2002
- 2002-01-02 DE DE10200050A patent/DE10200050A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912077A (en) * | 1988-07-15 | 1990-03-27 | Corning Incorporated | Catalytically active materials and method for their preparation |
| US5217936A (en) * | 1989-10-16 | 1993-06-08 | Haldor Topsoe A/S | Catalyst for preparing aldehyde |
| US6005143A (en) * | 1998-08-07 | 1999-12-21 | Air Products And Chemicals, Inc. | Use of a monolith catalyst for the hydrogenation of dinitrotoluene to toluenediamine |
| US6166283A (en) * | 1998-09-03 | 2000-12-26 | The Dow Chemical Company | On-line synthesis and regenerating of a catalyst used in autothermal oxidation |
| US6623707B1 (en) * | 2000-06-19 | 2003-09-23 | Corning Incorporated | Monolithic catalyst dehydrogenation reactor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3573746A4 (en) * | 2017-01-24 | 2020-10-21 | BASF Corporation | Monolithic catalysts for epoxidation |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10200050A1 (en) | 2003-02-06 |
| JP2002263476A (en) | 2002-09-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: SHELL OIL COMPANY, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WAMBAUGH, JAMES ALLEN;REEL/FRAME:013850/0203 Effective date: 20001114 |
|
| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |