CA1319703C - Method for making isobutyric acid - Google Patents
Method for making isobutyric acidInfo
- Publication number
- CA1319703C CA1319703C CA000579432A CA579432A CA1319703C CA 1319703 C CA1319703 C CA 1319703C CA 000579432 A CA000579432 A CA 000579432A CA 579432 A CA579432 A CA 579432A CA 1319703 C CA1319703 C CA 1319703C
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- reaction zone
- reaction mixture
- zone
- streams
- 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.)
- Expired - Fee Related
Links
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
- B01J19/2415—Tubular reactors
- B01J19/2425—Tubular reactors in parallel
-
- 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
- B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
- B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
-
- 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
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00085—Plates; Jackets; Cylinders
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
Abstract
ABSTRACT OF THE DISCLOSURE
A method for continuously reacting propylene and carbon monoxide in a hydrogen fluoride catalyst to produce, in the presence of water or an alcohol, isobutyric acid or an ester thereof, by introducing hydrogen fluoride, a liquid reagent, and a gaseous reagent into a first reaction chamber of a loop-type bubble column, conducting the low-density reaction mixture containing gas bubbles upwardly through a second reaction zone into a third reaction chamber wherein gas emerges from said reaction mixture to form a continuous gas phase and a more dense reaction mixture, and then conducting said continuous gas phase and more dense reaction mixture downwardly back to said first reaction chamber.
A method for continuously reacting propylene and carbon monoxide in a hydrogen fluoride catalyst to produce, in the presence of water or an alcohol, isobutyric acid or an ester thereof, by introducing hydrogen fluoride, a liquid reagent, and a gaseous reagent into a first reaction chamber of a loop-type bubble column, conducting the low-density reaction mixture containing gas bubbles upwardly through a second reaction zone into a third reaction chamber wherein gas emerges from said reaction mixture to form a continuous gas phase and a more dense reaction mixture, and then conducting said continuous gas phase and more dense reaction mixture downwardly back to said first reaction chamber.
Description
The present invention relates to a process for the continuous production of isobutyric acid, or its precursors or derivatives, by the Koch synthesis from approximately stoichiometric quantities of propylene, carbon monoxide, and, optionally, water or an alcohol t in liquid hydrogen fluoride as a Koch catalyst, under pressure and with a high degree of backmixing.
The prior art For the prior art process of this type disclosed in German patent 3,033,65S (corresponding to United States Patents 4,452,999 and 4,647,696), a bubble column or jet reactor has been proposed as suitable, provided that they will assure intimate contact of the gas phase with the liquid phase of the reagents and a high rate of circulation of the reaction mixture.
The object The present invention has as its object to permi~ these requirements to be met with a minimal of mechanical means for mixing and moving the liquid and gas phases. Sealing problems, which can easily arise at the packing glands of agitator shafts, are to be substantially eliminated.
The invention The invention provides a method for the continuous reaction, under pressure and with a high degree of backmixing, of approximately stoichiometric amounts of propylene~and carbon ~~ .
.
, , .
,: .
.
monoxide by the Koch synthesis in hydrogen fluoride as a catalyst to form, in the presence of water or an alcohol, isobutyric acid or an ester thereof. The method comprises introducing hydrogen fluoride and at least one gaseous and at least one liquid reagent into a first reaction zone to form a low-density reaction mixture containing gas bubbles. The low-density reaction mixture is conducted upwardly through a second reaction zone into a third reaction zone. In the third reaction zone, which zone is above the first and second reaction zones, bubbles emerge from the reaction mixture and collect to form a continuous gas phase, whereby the density of the reaction mixture increases.
Separately, the continuous gas phase and the reaction mixture of increased density from the third reaction zone are conducted downwardly into the first reaction zone where they are admixed with the hydrogen fluoride and liquid and gaseous reagent introduced into the first reaction zone. A constant reaction temperature is maintained. An amount of reaction mixture equal to the amount of reagents introduced into the first reaction zone is continuously withdrawn from at least one of the reaction zones.
Practice of the invention A reactor sui~able for carrying out the process of the invention is shown in the accompanying drawings, wherein Fig. 1 is a vertical sect10n through said reactor and Fig. 2 is a horizontal section through said reactor.
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..
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---" 131q70~
For the Koch synthesis of isobutyric acid from one molar part each of propylene, carbon monoxide, and water, hydrogen fluoride is charged to the reac-tion continuously as the Koch ca-talyst in a molar amount from 5 to 15 times that of the other components of the feed, especially propylene. At the prevailing pressure, generally from 50 to 150 bar, hydrogen fluoride is liquid even when introduced at a temperature of 60C.
Propylene may be introduced either in the liquid or gaseous state. Water is introduced in liquid form; carbon monoxide as a gas. The gas phase in the reac-tor consis-ts predominantly of carbon monoxide, present in excess, and of hydrogen fIuoride in accordance with i-ts par-tial pressure at the reaction-temperature.
The vapor pressures of propylene and water are negligible under steady state conditions in view of the small quantity.
When an isobutyric acid ester is being produced, the appropriate alcohol, for example methanol, is used in place of water. In place of the aforesaid starting substances, their addition products may be used in whole or in part, for example isopropanol or diisopropanol ether in place of propylene and water, formic acid in place of carbon monoxide and water, or isopropyl fluoride in place of propylene and hydrogen fluoride.
Similarly, addition products of methanol or of other alcohols may be used. Under the reaction conditions, all of -the addition products named are unstable and give the same reaction mixture as the components used per se.
The reaction product withdrawn is a liquid solution of isobutyric acid or its ester, or optionally its anhydride or _3_ ~
:
::
I
,:
. ~: : : : -:
:~ ` : :
fluoride, in hydrogen fluoride. The gas phase is exchanged only to the exten-t necessary for the removal of gaseous contaminants such as hydrogen or propane. Carbon monoxide is charged a-t the rate it is consumed. For a high yield and high selectivity for isobutyric acid, it is advantageous to maintain the concentra-tion of propylene and water or alcohol in the second to fourth reaction charnbers at less than 1 percent by weight, or less than 5 mole percent, based on the liquid phase. This will require, in addition to an appropriate feed rate, a high degree of backmixing of the reaction mixture, that is there should be no accumulation of starting materials downstream from the point of their introduction.
In accordance with the invention, this goal is a-ttained by dividing the total reaction space into four partial reaction spaces (volumes, zones, or chambers). In Fig. 1, these are designated as I, Il, III, and IV, respectively. In the preferred embodiment shown in Figs. 1 and 2, reac-tion chamber I is bounded by concave pressure resistant bottom 2 of reactor 1 and by tube support floor 3. A mixture of liquid and gaseous star-ting materials is fed into this reaction chamber through line 4.
Because at least one constituent of the reaction mixture is gaseous, a bubble-containing layer of reduced density collects under floor 3 and rises through the floor into superjacent reaction space II. The latter is preferably divided into a plurality of parallel, vertically disposed bubble columns. These discharge into reaction chamber III, which like reac-tor space I
is bounded by tube support ceiling 5 and domed cover 6. The ?
.
... . .
.
,~: : ~. : . , 13~9703 bubble columns project by tube extensions 7 somewhat beyond ceiling 5 so that a bubble free liquid layer of the reaction mixture is able to accumulate over ceiling 5. The gas bubbles emerging -from the reaction mixture collect in the upper region of reaction space III to form coherent gas phase 8. The specifically heavier (more dense) bubble free liquid phase descends through tube support ceiling 5 into reaction space IV, which is also preferable divided into a plurality of vertical tubes. These tubes terminate in extensions g below tube support floor 3 in reaction charnber I, so that the bubble-containing layer in said chamber cannot enter into the tubes.
Since the bubble-containing reaction mixture occupies a larger volume in reaction space II than does the bubble free mixture in reaction space IV, the cross sectional area of the latter may be smaller. The cross sectional area of the individual tubes being equal, the number of individual tubes in reactions spaces II and IV may bear a relation to one another of about 2 : 1. A hexagonal layout of the tubes will be appropriate, as shown in Fig. 2, wherein tubes of reaction space II are symbolized by the presence therein of circular bubbles.
The tubes are enclosed in cylindrical shell ~O, which need not be pressure resistant if the tubes themselves are pressure resistant. For dissipation of the heat of reaction and maintenance of a uniform reaction temperature, a coolant, which i enters and leaves through pipe connections 11 and 12, respectively, and which preferably has a lower pressure than the reaction med1um, flows around the tubes. The coolant may be :: . : : : : , :: : . .: - ~ :
, :
, :
. : , , , ~ : :
repeatedly deflected by means of baffle pla-tes 13.
From gas space 8 in reaction chamber III, the gas phase flows through pressure line 14 outside of the reactor to mixing chamber 15. There it is drawn in by the liquid phase consisting of the con-tinously fed-in liquid starting materials which flow at high velocity from nozzle 16 into the pipe, and is entrained into the reactor. To permi-t the entrained gas phase to be piped into reaction chamber I against the hydros-tatic pressure of -the reaction rnixture, the liquid phase must enter mixing nozzle 16 under a pressure that is substantially higher than the pressure in the reaetor. Furthermore, earbon monoxide is introdueed through line 17 or injected into line 14 at the rate at whieh it is eonsumed. At bottom 2 of reaction space I, bubble-free reaetion mixture is eontinuously withdrawn as product -through line 18.
If the rate of cireulation is to be variable, a gas eireulation pump (not shown) may be installed in pressure line 14. In plaee of mixing nozzle 15, another means may be ehosen for introdueing the gas being reeycled in pressure line 14 into the first reaction chamber and dispersing it in the reaction mixture. For example, a perforated plate or a plurality of gas nozzles may be provided on the underside of the first reaction spaee for the introduetion of fresh gas and of recycIed gas. The liquid starting materials can then be fed directly to the first reac-tion zone.
All components whieh eome into eontaet with the reaetion rnixture should be constructed of a material having ,: ' , :
--`'` 131q703 adequate corrosion and pressure resistance. According to German patent 3,139,653, suitablernaterials are, in addition to aluminum and nickel, some particularly corrosion resistant nickel-chromium-iron alloys (30-50% Ni, 20-30% Cr, 18-50% Fe).
Advantages Reaction zone II acts as a bubble column which provides not only for intimate mixing of the liquid and gaseous phases of the reaction mixture, but also for continuous circulation of the liquid phase through all four reaction zones. Circulation is brought about by the difference in density be-tween the low-density bubble-containing liquid phase in reaction zone II and the more dense bubble free liquid phase in reaction zone IV. The density difference results in a continuous ascent of -the liquid phase in reaction space II and descent of the liquid phase in reaction space IV.
In accordance with a preferred embodiment, the gas phase separated in reaction space III from the liquid phase is entrained without mechanical circulating means by the liquid starting materials flowing through a mixing nozzle and is recycled to reac-tion chamber I. Thus, there is no need for a circulating pump for the gas phase, either.
Since mechanical agitating and circulating means are dispensed with, a saving in equipment costs is realized. What is more important, -the corrosion and sealing problems which the extremely aggresslve reaction medium would inevitably create for conventional agitating and circulating equipment are completely avoided.
, .: :
The prior art For the prior art process of this type disclosed in German patent 3,033,65S (corresponding to United States Patents 4,452,999 and 4,647,696), a bubble column or jet reactor has been proposed as suitable, provided that they will assure intimate contact of the gas phase with the liquid phase of the reagents and a high rate of circulation of the reaction mixture.
The object The present invention has as its object to permi~ these requirements to be met with a minimal of mechanical means for mixing and moving the liquid and gas phases. Sealing problems, which can easily arise at the packing glands of agitator shafts, are to be substantially eliminated.
The invention The invention provides a method for the continuous reaction, under pressure and with a high degree of backmixing, of approximately stoichiometric amounts of propylene~and carbon ~~ .
.
, , .
,: .
.
monoxide by the Koch synthesis in hydrogen fluoride as a catalyst to form, in the presence of water or an alcohol, isobutyric acid or an ester thereof. The method comprises introducing hydrogen fluoride and at least one gaseous and at least one liquid reagent into a first reaction zone to form a low-density reaction mixture containing gas bubbles. The low-density reaction mixture is conducted upwardly through a second reaction zone into a third reaction zone. In the third reaction zone, which zone is above the first and second reaction zones, bubbles emerge from the reaction mixture and collect to form a continuous gas phase, whereby the density of the reaction mixture increases.
Separately, the continuous gas phase and the reaction mixture of increased density from the third reaction zone are conducted downwardly into the first reaction zone where they are admixed with the hydrogen fluoride and liquid and gaseous reagent introduced into the first reaction zone. A constant reaction temperature is maintained. An amount of reaction mixture equal to the amount of reagents introduced into the first reaction zone is continuously withdrawn from at least one of the reaction zones.
Practice of the invention A reactor sui~able for carrying out the process of the invention is shown in the accompanying drawings, wherein Fig. 1 is a vertical sect10n through said reactor and Fig. 2 is a horizontal section through said reactor.
~ i; !,;
~' . ' . ', ' ' ' ' ' . ' - ~ .
..
~' ' ' ~ . , ' , ' , , ..
---" 131q70~
For the Koch synthesis of isobutyric acid from one molar part each of propylene, carbon monoxide, and water, hydrogen fluoride is charged to the reac-tion continuously as the Koch ca-talyst in a molar amount from 5 to 15 times that of the other components of the feed, especially propylene. At the prevailing pressure, generally from 50 to 150 bar, hydrogen fluoride is liquid even when introduced at a temperature of 60C.
Propylene may be introduced either in the liquid or gaseous state. Water is introduced in liquid form; carbon monoxide as a gas. The gas phase in the reac-tor consis-ts predominantly of carbon monoxide, present in excess, and of hydrogen fIuoride in accordance with i-ts par-tial pressure at the reaction-temperature.
The vapor pressures of propylene and water are negligible under steady state conditions in view of the small quantity.
When an isobutyric acid ester is being produced, the appropriate alcohol, for example methanol, is used in place of water. In place of the aforesaid starting substances, their addition products may be used in whole or in part, for example isopropanol or diisopropanol ether in place of propylene and water, formic acid in place of carbon monoxide and water, or isopropyl fluoride in place of propylene and hydrogen fluoride.
Similarly, addition products of methanol or of other alcohols may be used. Under the reaction conditions, all of -the addition products named are unstable and give the same reaction mixture as the components used per se.
The reaction product withdrawn is a liquid solution of isobutyric acid or its ester, or optionally its anhydride or _3_ ~
:
::
I
,:
. ~: : : : -:
:~ ` : :
fluoride, in hydrogen fluoride. The gas phase is exchanged only to the exten-t necessary for the removal of gaseous contaminants such as hydrogen or propane. Carbon monoxide is charged a-t the rate it is consumed. For a high yield and high selectivity for isobutyric acid, it is advantageous to maintain the concentra-tion of propylene and water or alcohol in the second to fourth reaction charnbers at less than 1 percent by weight, or less than 5 mole percent, based on the liquid phase. This will require, in addition to an appropriate feed rate, a high degree of backmixing of the reaction mixture, that is there should be no accumulation of starting materials downstream from the point of their introduction.
In accordance with the invention, this goal is a-ttained by dividing the total reaction space into four partial reaction spaces (volumes, zones, or chambers). In Fig. 1, these are designated as I, Il, III, and IV, respectively. In the preferred embodiment shown in Figs. 1 and 2, reac-tion chamber I is bounded by concave pressure resistant bottom 2 of reactor 1 and by tube support floor 3. A mixture of liquid and gaseous star-ting materials is fed into this reaction chamber through line 4.
Because at least one constituent of the reaction mixture is gaseous, a bubble-containing layer of reduced density collects under floor 3 and rises through the floor into superjacent reaction space II. The latter is preferably divided into a plurality of parallel, vertically disposed bubble columns. These discharge into reaction chamber III, which like reac-tor space I
is bounded by tube support ceiling 5 and domed cover 6. The ?
.
... . .
.
,~: : ~. : . , 13~9703 bubble columns project by tube extensions 7 somewhat beyond ceiling 5 so that a bubble free liquid layer of the reaction mixture is able to accumulate over ceiling 5. The gas bubbles emerging -from the reaction mixture collect in the upper region of reaction space III to form coherent gas phase 8. The specifically heavier (more dense) bubble free liquid phase descends through tube support ceiling 5 into reaction space IV, which is also preferable divided into a plurality of vertical tubes. These tubes terminate in extensions g below tube support floor 3 in reaction charnber I, so that the bubble-containing layer in said chamber cannot enter into the tubes.
Since the bubble-containing reaction mixture occupies a larger volume in reaction space II than does the bubble free mixture in reaction space IV, the cross sectional area of the latter may be smaller. The cross sectional area of the individual tubes being equal, the number of individual tubes in reactions spaces II and IV may bear a relation to one another of about 2 : 1. A hexagonal layout of the tubes will be appropriate, as shown in Fig. 2, wherein tubes of reaction space II are symbolized by the presence therein of circular bubbles.
The tubes are enclosed in cylindrical shell ~O, which need not be pressure resistant if the tubes themselves are pressure resistant. For dissipation of the heat of reaction and maintenance of a uniform reaction temperature, a coolant, which i enters and leaves through pipe connections 11 and 12, respectively, and which preferably has a lower pressure than the reaction med1um, flows around the tubes. The coolant may be :: . : : : : , :: : . .: - ~ :
, :
, :
. : , , , ~ : :
repeatedly deflected by means of baffle pla-tes 13.
From gas space 8 in reaction chamber III, the gas phase flows through pressure line 14 outside of the reactor to mixing chamber 15. There it is drawn in by the liquid phase consisting of the con-tinously fed-in liquid starting materials which flow at high velocity from nozzle 16 into the pipe, and is entrained into the reactor. To permi-t the entrained gas phase to be piped into reaction chamber I against the hydros-tatic pressure of -the reaction rnixture, the liquid phase must enter mixing nozzle 16 under a pressure that is substantially higher than the pressure in the reaetor. Furthermore, earbon monoxide is introdueed through line 17 or injected into line 14 at the rate at whieh it is eonsumed. At bottom 2 of reaction space I, bubble-free reaetion mixture is eontinuously withdrawn as product -through line 18.
If the rate of cireulation is to be variable, a gas eireulation pump (not shown) may be installed in pressure line 14. In plaee of mixing nozzle 15, another means may be ehosen for introdueing the gas being reeycled in pressure line 14 into the first reaction chamber and dispersing it in the reaction mixture. For example, a perforated plate or a plurality of gas nozzles may be provided on the underside of the first reaction spaee for the introduetion of fresh gas and of recycIed gas. The liquid starting materials can then be fed directly to the first reac-tion zone.
All components whieh eome into eontaet with the reaetion rnixture should be constructed of a material having ,: ' , :
--`'` 131q703 adequate corrosion and pressure resistance. According to German patent 3,139,653, suitablernaterials are, in addition to aluminum and nickel, some particularly corrosion resistant nickel-chromium-iron alloys (30-50% Ni, 20-30% Cr, 18-50% Fe).
Advantages Reaction zone II acts as a bubble column which provides not only for intimate mixing of the liquid and gaseous phases of the reaction mixture, but also for continuous circulation of the liquid phase through all four reaction zones. Circulation is brought about by the difference in density be-tween the low-density bubble-containing liquid phase in reaction zone II and the more dense bubble free liquid phase in reaction zone IV. The density difference results in a continuous ascent of -the liquid phase in reaction space II and descent of the liquid phase in reaction space IV.
In accordance with a preferred embodiment, the gas phase separated in reaction space III from the liquid phase is entrained without mechanical circulating means by the liquid starting materials flowing through a mixing nozzle and is recycled to reac-tion chamber I. Thus, there is no need for a circulating pump for the gas phase, either.
Since mechanical agitating and circulating means are dispensed with, a saving in equipment costs is realized. What is more important, -the corrosion and sealing problems which the extremely aggresslve reaction medium would inevitably create for conventional agitating and circulating equipment are completely avoided.
, .: :
Claims (7)
1. A method for the continuous reaction, under pressure and with a high degree of backmixing, of approximately stoichiometric amounts of propylene and carbon monoxide by the Koch synthesis in hydrogen fluoride as a catalyst to form, in the presence of water or an alcohol, isobutyric acid or an ester thereof, which method comprises (A) introducing hydrogen fluoride and at least one gaseous and at least one liquid reagent into a first reaction zone to forms a low-density reaction mixture containing gas bubbles;
(b) conducting said low-density reaction mixture upwardly through a second reaction zone into (c) a third reaction zone, above said first and second reaction zones, in which third reaction zone bubbles emerge from said reaction mixture and collect to form a continuous gas phase, whereby the density of the reaction mixture increases; and (d) separately conducting said continuous gas phase and the reaction mixture of increased density from said third reaction zone downwardly into said first reaction zone where they are admixed with the hydrogen fluoride and liquid and gaseous reagent introduced into said first reaction zone, maintaining a constant reaction temperature and continuously withdrawing from at least one of said reaction zones an amount of reaction mixture equal to the amount of reagents introduced into said first reaction zone.
(b) conducting said low-density reaction mixture upwardly through a second reaction zone into (c) a third reaction zone, above said first and second reaction zones, in which third reaction zone bubbles emerge from said reaction mixture and collect to form a continuous gas phase, whereby the density of the reaction mixture increases; and (d) separately conducting said continuous gas phase and the reaction mixture of increased density from said third reaction zone downwardly into said first reaction zone where they are admixed with the hydrogen fluoride and liquid and gaseous reagent introduced into said first reaction zone, maintaining a constant reaction temperature and continuously withdrawing from at least one of said reaction zones an amount of reaction mixture equal to the amount of reagents introduced into said first reaction zone.
2. A method as in Claim 1 wherein said continuous gas phase collected in said third reaction zone is entrained into liquid reagent entering said first reaction zone, whereby said gas phase is conducted from said third zone to said first zone without the use of mechanical circulating means.
3. A method as in Claim 1 wherein said low-density reaction mixture conducted upwardly through said second reaction zone is divided into a plurality of streams.
4. A method as in Claim 3 wherein said reaction mixture of increased density conducted downwardly through said fourth reaction zone is divided into a plurality of streams.
5. A method as in Claim 4 wherein the number of streams in said fourth reaction zone is half as large as the number of streams in said second reaction zone, and wherein said streams are in a vertical, parallel, hexagonal packing arrangement wherein each partial stream of said fourth reaction zone is bounded by six partial streams of said second reaction zone.
6. A method as in Claim 4 wherein the reaction temperature in said first and fourth reaction zones is maintained by surrounding said partial streams therein with a coolant.
7. A method as in Claim 6 wherein said coolant has a pressure lower than that of the reaction mixture in said second and fourth reaction zones.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3733729.7 | 1987-10-06 | ||
| DE19873733729 DE3733729A1 (en) | 1987-10-06 | 1987-10-06 | CONTINUOUS METHOD FOR PRODUCING ISOBUTTERIC ACID |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1319703C true CA1319703C (en) | 1993-06-29 |
Family
ID=6337703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000579432A Expired - Fee Related CA1319703C (en) | 1987-10-06 | 1988-10-05 | Method for making isobutyric acid |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0310878B1 (en) |
| JP (1) | JPH01128955A (en) |
| CA (1) | CA1319703C (en) |
| DE (2) | DE3733729A1 (en) |
| ES (1) | ES2028224T3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650536A (en) | 1992-12-17 | 1997-07-22 | Exxon Chemical Patents Inc. | Continuous process for production of functionalized olefins |
| US5717039A (en) | 1992-12-17 | 1998-02-10 | Exxon Chemical Patents Inc. | Functionalization of polymers based on Koch chemistry and derivatives thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4100420A1 (en) * | 1991-01-09 | 1992-07-16 | Roehm Gmbh | CONTINUOUS METHOD FOR THE PRODUCTION OF ISOBUTTERIC ACID BY KOCH'S SYNTHESIS |
| EP1201298A1 (en) | 2000-10-24 | 2002-05-02 | Urea Casale S.A. | Carbamate condensation unit |
| CN100347284C (en) * | 2005-05-20 | 2007-11-07 | 清华大学 | Airlift circulating reactor needing no foreign gas |
| EA202190175A1 (en) | 2018-09-06 | 2021-06-25 | Публичное акционерное общество "СИБУР Холдинг" | BUBBLE SHELL-TUBE APPARATUS |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0031886B1 (en) * | 1979-12-20 | 1984-04-11 | Röhm Gmbh | Process for the production of isobutyric acid or its lower alkyl esters |
| DE3139653A1 (en) * | 1981-10-06 | 1983-04-21 | Röhm GmbH, 6100 Darmstadt | USE OF METAL DEVICES IN THE IMPLEMENTATION AND PROCESSING OF HYDROFLUORINE AND ORGANIC CARBONIC ACIDS OR MIXTURES CONTAINING CARBON |
-
1987
- 1987-10-06 DE DE19873733729 patent/DE3733729A1/en not_active Withdrawn
-
1988
- 1988-09-22 EP EP88115603A patent/EP0310878B1/en not_active Expired - Lifetime
- 1988-09-22 ES ES198888115603T patent/ES2028224T3/en not_active Expired - Lifetime
- 1988-09-22 DE DE8888115603T patent/DE3867407D1/en not_active Expired - Lifetime
- 1988-10-05 CA CA000579432A patent/CA1319703C/en not_active Expired - Fee Related
- 1988-10-06 JP JP63251021A patent/JPH01128955A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650536A (en) | 1992-12-17 | 1997-07-22 | Exxon Chemical Patents Inc. | Continuous process for production of functionalized olefins |
| US5717039A (en) | 1992-12-17 | 1998-02-10 | Exxon Chemical Patents Inc. | Functionalization of polymers based on Koch chemistry and derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0310878A1 (en) | 1989-04-12 |
| DE3867407D1 (en) | 1992-02-13 |
| ES2028224T3 (en) | 1992-07-01 |
| DE3733729A1 (en) | 1989-04-20 |
| EP0310878B1 (en) | 1992-01-02 |
| JPH01128955A (en) | 1989-05-22 |
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