CA1065341A - Oxidation of propylene and isobutylene to obtain the corresponding unsaturated aldehydes and acids - Google Patents
Oxidation of propylene and isobutylene to obtain the corresponding unsaturated aldehydes and acidsInfo
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- CA1065341A CA1065341A CA246,905A CA246905A CA1065341A CA 1065341 A CA1065341 A CA 1065341A CA 246905 A CA246905 A CA 246905A CA 1065341 A CA1065341 A CA 1065341A
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- catalyst
- catalytic material
- propylene
- oxidation
- isobutylene
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00212—Plates; Jackets; Cylinders
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00823—Mixing elements
- B01J2208/00858—Moving elements
- B01J2208/00876—Moving elements outside the bed, e.g. rotary mixer
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
OXIDATION OF PROPYLENE AND ISOBUTYLENE TO
OBTAIN THE CORRESPONDING UNSATURATED
ALDEHYDES AND ACIDS
ABSTRACT OF THE DISCLOSURE
Very desirable temperature control in the oxidation of propylene or isobutylene in a fixed-bed, tubular reactor is obtained by using an oxidation catalyst having two physical forms. me first catalyst which initially contacts the reactants is an essentially inert support having a strongly adhering coat of a catalytic material, and the second catalyst that contacts the reactants after contact with the first catalyst consists essentially of the catalytic material.
OBTAIN THE CORRESPONDING UNSATURATED
ALDEHYDES AND ACIDS
ABSTRACT OF THE DISCLOSURE
Very desirable temperature control in the oxidation of propylene or isobutylene in a fixed-bed, tubular reactor is obtained by using an oxidation catalyst having two physical forms. me first catalyst which initially contacts the reactants is an essentially inert support having a strongly adhering coat of a catalytic material, and the second catalyst that contacts the reactants after contact with the first catalyst consists essentially of the catalytic material.
Description
BACKGROUND OF THE INVENTION
There are a large number of catalysts known to be effectlve ln the oxldatlon Or propylene or lsobutylene.
m e present lnventlon 18 not a new catalyst but a method of adaptlng the known cataly~ts to an lmproved precess ror preparlng un~aturated aldehydes and aclds from the3e oleflns, In a flxed_bed oxldation reactlon, very slgnl~lcant problems Or heat generatlon are encountered at hi~h reed rates because Or the exothermlc nature of the reactlon, To allow for the dl~slpatlon of the heat generated, low rates o~ throughput and small dlameter tublng have been employed, The present lnventlon 1~ dlrected toward the ~olution Or thl~ problem by a more economlcally acceptable technique.
_ 1 -(4844) ~ S3 4~
SUMMARY OF THE INVENTION
.
It ha~ now been dlecoverod ln the proce~s ~or pr~parlng unsAturated aldehyde~ and aclds by the r~actlon Or a mlxture of propylene or lssbutylone and molecular oxygen ln the presence o~ an oxldatlon cstalyot ln a ~lxed-bed reactor contalnlng one or more tubes, the l~provement comprislng using two catalyMts ln th~ tubes o~ the rlxed-bed reactor--the rlrst catalyst belng a cataly~t comprl~lng an ea~entlally lnert 3upport material wlth an outer surrace and a coatlng o~ fl catalytlc materlal ~trongly adherlng to the outer cur~ace Or th~ ~upport and the ~econd catalyst belng a cntalyst con~l~tlng essentlally Or the catalytlc materlal and arranglng th~ catalysts ln the tubes of the flxed-bed reactor ln such a manner thfit the rlrst catalyst contact~
the reactant~ rlrst end the second catalyst contact~ the roactant~ sub~equent to contact with tho rlrst catalyet.
The present lnventlon makes t~p~raturo control Or the exothermlc reaction very convenlent, whlle at the same tlme hlgh converslons Or the ole~lns are m~lntalned.
me baslc thrust Or the lnventlon 1~ the use o~
two catalysts!!havlng dlrrerent phy~lcal ~orms. me rlr~t CatalyBt 18 a coated catalyst, and the ~econd c~talyst consl~ts essentlally Or the catalytlc materlal.
The term "lnert support" me~n~ ~ ~upport materlal that when placed ln the reactor by ltsel~ and rm under the reactlon condltions o~ the oxldatlon, glveh les~ than about 10% per pa~s converslon to the deslred aldehyde.
me term "catalytlc material" m~an~ the actlve catalytlc lngredlent~ optlonally contalnlng a support materlal, such as slllca dlspersed throughout the actlv¢ lngredlent6.
(4844) As noted above, the pre~ent lnvention 1~ not n~w ~ctlve cRtalyt1c ingredlent~, but rath6r lt 1~ a ~ethod of adapting c&taly3ts known in the art to a suitable flxcd-bed proce~s. Thlu process o~ the lnvention uses fi coated S cataly~t a8 the flrst cataly~t ~nd a catalyst consl~ting essentlally of the catalytlc matorlal a~ the e~cond cataly~t~
The rlrst cataly~t i8 a coated catalyet con~l~tlng of an e~entially in~rt 6upport ha~lng an out~r co~tlng Or catalytlc materlal. The lnert support may be any materlal that 1~ not actlve ln the ox~datlon reactlon. Suitable ex~mples Or ees~ntlQlly lnart support materlals lnclude:
sillca, alumln~, Alundum, silicon carblde, boron phosphato, zirconls and the llke Ihe lnert aupport mu~t be at lesst partlally porou~.
The essentially inert support may be about 0.1 cm. or largcr. Whlle there la no theoretical uppor limlt on the ~lze, the lnert support i8 generally les~ than
There are a large number of catalysts known to be effectlve ln the oxldatlon Or propylene or lsobutylene.
m e present lnventlon 18 not a new catalyst but a method of adaptlng the known cataly~ts to an lmproved precess ror preparlng un~aturated aldehydes and aclds from the3e oleflns, In a flxed_bed oxldation reactlon, very slgnl~lcant problems Or heat generatlon are encountered at hi~h reed rates because Or the exothermlc nature of the reactlon, To allow for the dl~slpatlon of the heat generated, low rates o~ throughput and small dlameter tublng have been employed, The present lnventlon 1~ dlrected toward the ~olution Or thl~ problem by a more economlcally acceptable technique.
_ 1 -(4844) ~ S3 4~
SUMMARY OF THE INVENTION
.
It ha~ now been dlecoverod ln the proce~s ~or pr~parlng unsAturated aldehyde~ and aclds by the r~actlon Or a mlxture of propylene or lssbutylone and molecular oxygen ln the presence o~ an oxldatlon cstalyot ln a ~lxed-bed reactor contalnlng one or more tubes, the l~provement comprislng using two catalyMts ln th~ tubes o~ the rlxed-bed reactor--the rlrst catalyst belng a cataly~t comprl~lng an ea~entlally lnert 3upport material wlth an outer surrace and a coatlng o~ fl catalytlc materlal ~trongly adherlng to the outer cur~ace Or th~ ~upport and the ~econd catalyst belng a cntalyst con~l~tlng essentlally Or the catalytlc materlal and arranglng th~ catalysts ln the tubes of the flxed-bed reactor ln such a manner thfit the rlrst catalyst contact~
the reactant~ rlrst end the second catalyst contact~ the roactant~ sub~equent to contact with tho rlrst catalyet.
The present lnventlon makes t~p~raturo control Or the exothermlc reaction very convenlent, whlle at the same tlme hlgh converslons Or the ole~lns are m~lntalned.
me baslc thrust Or the lnventlon 1~ the use o~
two catalysts!!havlng dlrrerent phy~lcal ~orms. me rlr~t CatalyBt 18 a coated catalyst, and the ~econd c~talyst consl~ts essentlally Or the catalytlc materlal.
The term "lnert support" me~n~ ~ ~upport materlal that when placed ln the reactor by ltsel~ and rm under the reactlon condltions o~ the oxldatlon, glveh les~ than about 10% per pa~s converslon to the deslred aldehyde.
me term "catalytlc material" m~an~ the actlve catalytlc lngredlent~ optlonally contalnlng a support materlal, such as slllca dlspersed throughout the actlv¢ lngredlent6.
(4844) As noted above, the pre~ent lnvention 1~ not n~w ~ctlve cRtalyt1c ingredlent~, but rath6r lt 1~ a ~ethod of adapting c&taly3ts known in the art to a suitable flxcd-bed proce~s. Thlu process o~ the lnvention uses fi coated S cataly~t a8 the flrst cataly~t ~nd a catalyst consl~ting essentlally of the catalytlc matorlal a~ the e~cond cataly~t~
The rlrst cataly~t i8 a coated catalyet con~l~tlng of an e~entially in~rt 6upport ha~lng an out~r co~tlng Or catalytlc materlal. The lnert support may be any materlal that 1~ not actlve ln the ox~datlon reactlon. Suitable ex~mples Or ees~ntlQlly lnart support materlals lnclude:
sillca, alumln~, Alundum, silicon carblde, boron phosphato, zirconls and the llke Ihe lnert aupport mu~t be at lesst partlally porou~.
The essentially inert support may be about 0.1 cm. or largcr. Whlle there la no theoretical uppor limlt on the ~lze, the lnert support i8 generally les~ than
2 cm. ln dlameter.
The catalytlc materlal may be coated onto lnert support by partlally wettlng the ~upport wlth water or other llquld and contactlng the partlally wet ~upport materlal wlth a powder of the actlve catalytlc materlal, preferably ln a rolllng motlon. Uslng thls technlque, the c~talytlc materlal forms a strongly adherlng coat on the ~upport materlal. In the preferred preparation of the flret catalyst, ~pherlcal supports are u~ed to obtaln preferred spherlcal first catalysts The relatlve amounts Or th~ lnert ~upport and catalytlc matorlal may vary widely Ihe co~tlng o~ cataly~lc ~4844) ~(3~ ~ ~ L~
materl~l may bc rQlatlv~ly thln or r~th~r thlck. In ~
prer~rred pr~ctlce o~ th~ inYention~ thc rlr8~ cataly~t contaln~ about 5 to a~ou~ 60% by w~l~h~ Or tho catalytlc m~terial.
Th~ s~cond cataly~t con~ist~ cfi~entl~lly Or thc c&tal~tic materlal, Th~ae cataly8t8 ~8 noted m~y contaln a support mat~rial ~lsperscd throughout the catQlyst.
These c~talyst~ are normally tha c~aly8t8 that have becn ~ploycd alono ln oxidatlon r~actlon~. ~arlow ~orm~ o~
thlc ~econd c~taly~t such aD tablct~, aphercs ~nd p~llot~
sr~ known.
Th- t~rm "con~i~tlng e0a~ntlally o~" in thc cont~xt Or thls lnvontlon, relate~ to tho c~taly~t partlclo.
m us~ ~or ~xampl~, p~rtlcl~s o~ catalytic materlal physlc~lly mlxed wlth p~rtlcle~ o~ a solid dilucn~ would m~et thl~
criterlon.
In Q pre~errcd practice of tho lnventlon, tho catalytic m~tcrlsl e~ployed ln the rlr~t catalyst and the catalyst materlal ~mployed in the s~cond catalyst are e~entlally thc sams. Po~sible lnter~er~nce o~ ono active ingredient with unother 1~ thus ellmlnated.
The relatlve amounts o~ the flrst catalyst end second cat~lyst may v~ry wldely. Enough Or the ~lr~t c~t~ly~t should b~ ~ployed to control the t~mper~ture Or th~ reactlon.
EnouBh o~ the ~econd cstaly~t should be employed ~o a~ure th~t th~ con~ers~on of the olerln 1~ st a de~lrably hi6h (about 90~) lev~l. In a pref~rred practlce o~ th~ lnv~ntion, about 10 to about 80~ by volu~e Or the r~actor tube contaln~
the rlr~t ca~aly~t.
-- 4 _ ( 4841~ ) 10~
As noted above J the actlve catalytlc lngredlenta may be selected ~rom any of the lngredlents ln the art.
In a preferred practlce o~ the lnventlon, the active lngredient~ of the catalytlc materlal ~re de~cribed by th~
~ormula Aa ~b Fec Bld M12 x wherein A i8 an ~lkali metal, ~lkallne earth metal~ Sm, Ta, Tl, In, Ga, B, P, As, Sb or mlxtures thereo~;
B is nlc~el, cobalt, magne~lum, manganese or mlxture thereor;
and whereln Q 1B a numSer Or 0 to about 8;
b 18 a number of 0 to about 20;
c 18 a nu~ber rrO~ about 0.1 to lS about 10;
d ie a number from about 0.01 to about 6; and x 18 the number Or oxygens requlred to satiæry the valence requlrements Or the other ~lemcnts present.
Of these cataly~ts, the pre~erred catalyqts contain nlckol, cobalt, magneslu~ mangane~e or mlxture thereof. This is accomplished ln the formula by settlng b equal to a po~ltlYe number. Also, catalyst~ contalning nlckel, cob~lt or mlxturcs thereor are especlally ~referred, l.e., where B 1~ cobalt, nlckel or mixture thereo~. Tho~e cataly~tæ contalnlng pot~slum are also preferred.
The reactlon of the present inventlon 18 run accordlng to the parameter~ descrlbed ln the art. The reQctsnts, cat~lyæts, reactlon cond~tions and the llke ~re those wlthin the range~ that are known. mc molar r~tlo Or molecular oxygen to olefin 18 about 0.7 to about 4 or more. The reactlon can be run at atmoæpheric, ~ubatmospherlc ( 484J~
L~)~S~ ~i or superQtmo~pherlc pre~sure, ~he temperature~ range rrom about 200 to about 600C., wlth temper~tures of 300 to about 500 C. being pre~rred. The contact time may r~nge up to about 20 seconds or morc.
The cataly~t ~yBtem Or the inventlon m~y be used aloneto produc~ the un~aturated aldehyde,or it could be u~ed in conJunctlon with a cataly~t system that convert~ the unsaturated aldehyde to the corresponding unQaturated acld.
The important a~pect o~ the inventlon i8 the v~ry de~lrable temperature control per~ltted at hlgh olefin conver~lons. mo~e desirable b2nefits are obtalned uslng the two catalyst ~y~tems of the inventlon.
DESCRIPTION OF THE DRAWING
Figure 1 shows a side-v~ew o~ a rixed-bed acroleln reactor. Flgure 2 shows a top-vlew Or the acroleln reactor.
Referring to Figure l, it iB seen that the reactor consists Or an outer ahell 1 containlng a plurality o~
tube~ 2. Each of the tubes contains a flrst cataly~t 3 and ~ second catalyst 4 in ~uch a manner that the reactant~
contact the first catalyst rlr~t.
The reactant~ are fed through condult 5 lnto manlfold 6 where the reactants are dlstributed evenly to the tubes 2. The products are collected ln manlrold 7 and pas~ed to recovery and purl~icatlon operations (not shown) by conduit 8, The reactor i8 equlpped wlth a ~tlrrer 2 that stlr~ heat transfer fluld 10. Heat tran~fer rluld 10 18 cooled by a heat exchange ~ystem 12, ~, 14 and l~ and returncd to the reactor shell, (48~4) SPECIFIC EMBOD~MENTS
. . . ~
Co~Farative Exam~le A Rnd Exam ~ es 1 and 2 _ Comparl~on Or a e c ca a y~t only to u~e o~
coated and tableted cataly~t.
A fixed_bed reactor was construct~d uslng 2,7 cm.
lnslde dlameter 8talnle88 ~teel tube, havlng 8 reaction zon~
4 meters long. A catalyst having the compositlon 87.5%
.lN12 554~5Fe3BlPo.sMol2ox and 17,5~ SiOx was prepar~d accordlng to U. S. 3,746,657. The cataly~t Wh~ denltrl~led at 425C., ~ormed lnto t~blet~ o~ 0.5 cm. dlameter ~nd calclned. Another catalyst of the ssme actlve lngredlent compositlon, but no slllca, was prepared and coated on 0.32 cm. dla~eter Alundum spheres. m 18 coating wa8 accompllshed by partlally w~ttlng the Alundum spheres with water, contactlng the 8pheres wlth a powder of the catalytlc materi~l ln a rolllng motion and drylng the coated ~upports. The coated cataly8t contalned 33.3~ by welght of the catalytlc materlal.
The coated catalyet was calc1ned ror two hours at 538C.
Compar~tive ExAmple A
The entlre reactlon zone of the roactor was filled with the tableted catalyst only. Non~ Or the coated catalyst was employed. Attempts to establl~h a stsble acroleln reactlon were made uslng a number of startup procedure~. None Or the startup technlques were success~ul ln establlshing a stable reactlon. In each case an uncontrollable tempsrsture lncrease was encountered, and the reaction was termlnated ~or sarety reasons, It wa~ determlned that the tableted c~talyst alon~
could not be run ln thls reactor un~er suitable reactant ~eed rates.
The catalytlc materlal may be coated onto lnert support by partlally wettlng the ~upport wlth water or other llquld and contactlng the partlally wet ~upport materlal wlth a powder of the actlve catalytlc materlal, preferably ln a rolllng motlon. Uslng thls technlque, the c~talytlc materlal forms a strongly adherlng coat on the ~upport materlal. In the preferred preparation of the flret catalyst, ~pherlcal supports are u~ed to obtaln preferred spherlcal first catalysts The relatlve amounts Or th~ lnert ~upport and catalytlc matorlal may vary widely Ihe co~tlng o~ cataly~lc ~4844) ~(3~ ~ ~ L~
materl~l may bc rQlatlv~ly thln or r~th~r thlck. In ~
prer~rred pr~ctlce o~ th~ inYention~ thc rlr8~ cataly~t contaln~ about 5 to a~ou~ 60% by w~l~h~ Or tho catalytlc m~terial.
Th~ s~cond cataly~t con~ist~ cfi~entl~lly Or thc c&tal~tic materlal, Th~ae cataly8t8 ~8 noted m~y contaln a support mat~rial ~lsperscd throughout the catQlyst.
These c~talyst~ are normally tha c~aly8t8 that have becn ~ploycd alono ln oxidatlon r~actlon~. ~arlow ~orm~ o~
thlc ~econd c~taly~t such aD tablct~, aphercs ~nd p~llot~
sr~ known.
Th- t~rm "con~i~tlng e0a~ntlally o~" in thc cont~xt Or thls lnvontlon, relate~ to tho c~taly~t partlclo.
m us~ ~or ~xampl~, p~rtlcl~s o~ catalytic materlal physlc~lly mlxed wlth p~rtlcle~ o~ a solid dilucn~ would m~et thl~
criterlon.
In Q pre~errcd practice of tho lnventlon, tho catalytic m~tcrlsl e~ployed ln the rlr~t catalyst and the catalyst materlal ~mployed in the s~cond catalyst are e~entlally thc sams. Po~sible lnter~er~nce o~ ono active ingredient with unother 1~ thus ellmlnated.
The relatlve amounts o~ the flrst catalyst end second cat~lyst may v~ry wldely. Enough Or the ~lr~t c~t~ly~t should b~ ~ployed to control the t~mper~ture Or th~ reactlon.
EnouBh o~ the ~econd cstaly~t should be employed ~o a~ure th~t th~ con~ers~on of the olerln 1~ st a de~lrably hi6h (about 90~) lev~l. In a pref~rred practlce o~ th~ lnv~ntion, about 10 to about 80~ by volu~e Or the r~actor tube contaln~
the rlr~t ca~aly~t.
-- 4 _ ( 4841~ ) 10~
As noted above J the actlve catalytlc lngredlenta may be selected ~rom any of the lngredlents ln the art.
In a preferred practlce o~ the lnventlon, the active lngredient~ of the catalytlc materlal ~re de~cribed by th~
~ormula Aa ~b Fec Bld M12 x wherein A i8 an ~lkali metal, ~lkallne earth metal~ Sm, Ta, Tl, In, Ga, B, P, As, Sb or mlxtures thereo~;
B is nlc~el, cobalt, magne~lum, manganese or mlxture thereor;
and whereln Q 1B a numSer Or 0 to about 8;
b 18 a number of 0 to about 20;
c 18 a nu~ber rrO~ about 0.1 to lS about 10;
d ie a number from about 0.01 to about 6; and x 18 the number Or oxygens requlred to satiæry the valence requlrements Or the other ~lemcnts present.
Of these cataly~ts, the pre~erred catalyqts contain nlckol, cobalt, magneslu~ mangane~e or mlxture thereof. This is accomplished ln the formula by settlng b equal to a po~ltlYe number. Also, catalyst~ contalning nlckel, cob~lt or mlxturcs thereor are especlally ~referred, l.e., where B 1~ cobalt, nlckel or mixture thereo~. Tho~e cataly~tæ contalnlng pot~slum are also preferred.
The reactlon of the present inventlon 18 run accordlng to the parameter~ descrlbed ln the art. The reQctsnts, cat~lyæts, reactlon cond~tions and the llke ~re those wlthin the range~ that are known. mc molar r~tlo Or molecular oxygen to olefin 18 about 0.7 to about 4 or more. The reactlon can be run at atmoæpheric, ~ubatmospherlc ( 484J~
L~)~S~ ~i or superQtmo~pherlc pre~sure, ~he temperature~ range rrom about 200 to about 600C., wlth temper~tures of 300 to about 500 C. being pre~rred. The contact time may r~nge up to about 20 seconds or morc.
The cataly~t ~yBtem Or the inventlon m~y be used aloneto produc~ the un~aturated aldehyde,or it could be u~ed in conJunctlon with a cataly~t system that convert~ the unsaturated aldehyde to the corresponding unQaturated acld.
The important a~pect o~ the inventlon i8 the v~ry de~lrable temperature control per~ltted at hlgh olefin conver~lons. mo~e desirable b2nefits are obtalned uslng the two catalyst ~y~tems of the inventlon.
DESCRIPTION OF THE DRAWING
Figure 1 shows a side-v~ew o~ a rixed-bed acroleln reactor. Flgure 2 shows a top-vlew Or the acroleln reactor.
Referring to Figure l, it iB seen that the reactor consists Or an outer ahell 1 containlng a plurality o~
tube~ 2. Each of the tubes contains a flrst cataly~t 3 and ~ second catalyst 4 in ~uch a manner that the reactant~
contact the first catalyst rlr~t.
The reactant~ are fed through condult 5 lnto manlfold 6 where the reactants are dlstributed evenly to the tubes 2. The products are collected ln manlrold 7 and pas~ed to recovery and purl~icatlon operations (not shown) by conduit 8, The reactor i8 equlpped wlth a ~tlrrer 2 that stlr~ heat transfer fluld 10. Heat tran~fer rluld 10 18 cooled by a heat exchange ~ystem 12, ~, 14 and l~ and returncd to the reactor shell, (48~4) SPECIFIC EMBOD~MENTS
. . . ~
Co~Farative Exam~le A Rnd Exam ~ es 1 and 2 _ Comparl~on Or a e c ca a y~t only to u~e o~
coated and tableted cataly~t.
A fixed_bed reactor was construct~d uslng 2,7 cm.
lnslde dlameter 8talnle88 ~teel tube, havlng 8 reaction zon~
4 meters long. A catalyst having the compositlon 87.5%
.lN12 554~5Fe3BlPo.sMol2ox and 17,5~ SiOx was prepar~d accordlng to U. S. 3,746,657. The cataly~t Wh~ denltrl~led at 425C., ~ormed lnto t~blet~ o~ 0.5 cm. dlameter ~nd calclned. Another catalyst of the ssme actlve lngredlent compositlon, but no slllca, was prepared and coated on 0.32 cm. dla~eter Alundum spheres. m 18 coating wa8 accompllshed by partlally w~ttlng the Alundum spheres with water, contactlng the 8pheres wlth a powder of the catalytlc materi~l ln a rolllng motion and drylng the coated ~upports. The coated cataly8t contalned 33.3~ by welght of the catalytlc materlal.
The coated catalyet was calc1ned ror two hours at 538C.
Compar~tive ExAmple A
The entlre reactlon zone of the roactor was filled with the tableted catalyst only. Non~ Or the coated catalyst was employed. Attempts to establl~h a stsble acroleln reactlon were made uslng a number of startup procedure~. None Or the startup technlques were success~ul ln establlshing a stable reactlon. In each case an uncontrollable tempsrsture lncrease was encountered, and the reaction was termlnated ~or sarety reasons, It wa~ determlned that the tableted c~talyst alon~
could not be run ln thls reactor un~er suitable reactant ~eed rates.
3 - 7 -. ~
(4844 ;5~41 Exam~l e s 1- 2 The same reactor ~ shown ln Comparative Example A
was ch~rged with a catalyst of coated catalyst and tableted cataly~t accordlng to the in~ention. The flr~t hal~ of the 5 reactlon tube closest to the reactor inlet wa8 charged wlth the coated cataly~t, and the second half of the reactlon tube wa~ charged with the tableted catalyst. Thi~ catalyst ~ystem was operated u~lng a feed of propylene/alr~steam Or l/7.5/6.
For the experlment of Example l, at a temperature of 345C.
and a ~pace velocity Or 1500 volumes of reactants at STP/
volume occupled by the catalyst/hour, the ~lngle pass yleld to useful products measured as the moles of acroleln and acryllc acid produced tlmes lO0 and dlvlded by the mole~ Or propylene fed wa~ 90.8~. Of the propylene fed, 96.3~ was converted. At 355C. and a space velocity o~ 1700 representlng Example 2, the slngle pass yleld was 89.4~ at a 95.5~ propylene conver~lon. This Example 2 had the greatest rate o~ productlvlty in a given time. In e~ch ca~e, the product W~B more th~n 80~ acrolein.
0 Example 3 - Dlfferent diameter tube and dlfferent percent coated.
A reaction tube of 2 cm. lnside dlameter,4 meters long was loaded wlth l/3 coated catalyst toward the inlot and 2/3 of the tableted catalyst ln the remalnder of tha tube. Using a temperature of 355C., a feed Or propylene/
alr/~team of l/8.6/6 and a space velocity of about 1300, the single p~88 converslon to u~eful products was 90.0~ with a propylene converslon of 95.5~. The difference between the temperature of the bath and the temperature of the catalyst bed was 58C.
_ 8 --(4844) 1 0 ~ ~ ~ 4 ~
In the ~me manner a8 chown by the ex~mplc above, lBobutylene 18 subs~ltuted ror the propylene in the reed and methacrolein and methacryllc acid are produced, Also, ln the same manner a~ shown abo~e for one psrt~cular catalyst, other cataly8t8 that are known to be useful for the oxldstlon of olefins are employed in coated rorm ln comblnatlon wlth the essentlally pure catalytlc materl~l to produce a de~lrablc ~ixed-bed oxidatlon proce~.
(4844 ;5~41 Exam~l e s 1- 2 The same reactor ~ shown ln Comparative Example A
was ch~rged with a catalyst of coated catalyst and tableted cataly~t accordlng to the in~ention. The flr~t hal~ of the 5 reactlon tube closest to the reactor inlet wa8 charged wlth the coated cataly~t, and the second half of the reactlon tube wa~ charged with the tableted catalyst. Thi~ catalyst ~ystem was operated u~lng a feed of propylene/alr~steam Or l/7.5/6.
For the experlment of Example l, at a temperature of 345C.
and a ~pace velocity Or 1500 volumes of reactants at STP/
volume occupled by the catalyst/hour, the ~lngle pass yleld to useful products measured as the moles of acroleln and acryllc acid produced tlmes lO0 and dlvlded by the mole~ Or propylene fed wa~ 90.8~. Of the propylene fed, 96.3~ was converted. At 355C. and a space velocity o~ 1700 representlng Example 2, the slngle pass yleld was 89.4~ at a 95.5~ propylene conver~lon. This Example 2 had the greatest rate o~ productlvlty in a given time. In e~ch ca~e, the product W~B more th~n 80~ acrolein.
0 Example 3 - Dlfferent diameter tube and dlfferent percent coated.
A reaction tube of 2 cm. lnside dlameter,4 meters long was loaded wlth l/3 coated catalyst toward the inlot and 2/3 of the tableted catalyst ln the remalnder of tha tube. Using a temperature of 355C., a feed Or propylene/
alr/~team of l/8.6/6 and a space velocity of about 1300, the single p~88 converslon to u~eful products was 90.0~ with a propylene converslon of 95.5~. The difference between the temperature of the bath and the temperature of the catalyst bed was 58C.
_ 8 --(4844) 1 0 ~ ~ ~ 4 ~
In the ~me manner a8 chown by the ex~mplc above, lBobutylene 18 subs~ltuted ror the propylene in the reed and methacrolein and methacryllc acid are produced, Also, ln the same manner a~ shown abo~e for one psrt~cular catalyst, other cataly8t8 that are known to be useful for the oxldstlon of olefins are employed in coated rorm ln comblnatlon wlth the essentlally pure catalytlc materl~l to produce a de~lrablc ~ixed-bed oxidatlon proce~.
Claims (10)
1. In the process for preparing unsaturated aldehydes and acids by the reaction of a mixture of propylene or isobutylene and molecular oxygen in the presence of an oxidation catalyst in a fixed-bed reactor containing one or more tubes, the improvement comprising using two catalysts in each of one or more of the tubes of the fixed-bed reactor--the first catalyst being a catalyst consisting of an essentially inert support material with an outer surface and coating of a catalytic material strongly adhering to the outer surface of the support and the second catalyst being a catalyst consisting essentially of the catalytic material and arranging the catalysts in the tube of the fixed-bed reactor in such a manner that the first catalyst contacts the reactants first and the second catalyst contacts the reactants subsequent to contact with the first catalyst.
2. The process of Claim 1 wherein the catalytic material of the first catalyst and the catalytic material of the second catalyst are substantially the same.
3. The process of Claim 1 wherein the first catalyst contains about 5 to about 60% catalytic material.
4. The process of Claim 1 wherein the reactor tubes contain about 10 to about 80% by volume of the first catalyst.
5. The process of Clalm 1 wherein the active ingredients of the catalytic material are described by the formula Aa Bb FeC Bid Mo12 Ox wherein A is an alkali metal, alkaline earth metal, Sm, Ta, Tl, In, Ga, B, P, As, Sb or mixtures thereof;
B is nickel, cobalt, magnesium, manganese or mixture thereof;
and wherein a is a number of 0 to about 8;
b is a number of 0 to about 20;
c is a number from about 0.1 to about 10;
d is a number from about 0.01 to about 6; and X is the number of oxygens required to satisfy the valence requirements of the other elements present.
B is nickel, cobalt, magnesium, manganese or mixture thereof;
and wherein a is a number of 0 to about 8;
b is a number of 0 to about 20;
c is a number from about 0.1 to about 10;
d is a number from about 0.01 to about 6; and X is the number of oxygens required to satisfy the valence requirements of the other elements present.
6. The process of Claim 5 wherein b in the formula is a positive number.
7. The process of Claim 6 wherein B is nickel, cobalt or mixture thereof.
8. The process of Claim 5 wherein A is potassium and a is a positive number.
9. The process of Claim 1 wherein the first catalyst is a spherical catalyst.
10. The process of Claim 5 wherein the catalyst material contains K0.1Ni2.5Co4.5Fe3BiP0.5Mo120x.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57012675A | 1975-04-21 | 1975-04-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1065341A true CA1065341A (en) | 1979-10-30 |
Family
ID=24278352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA246,905A Expired CA1065341A (en) | 1975-04-21 | 1976-03-02 | Oxidation of propylene and isobutylene to obtain the corresponding unsaturated aldehydes and acids |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS51127013A (en) |
| AT (1) | AT343091B (en) |
| BE (1) | BE839955A (en) |
| BR (1) | BR7602429A (en) |
| CA (1) | CA1065341A (en) |
| CH (1) | CH619442A5 (en) |
| CS (1) | CS193541B2 (en) |
| DD (1) | DD124592A5 (en) |
| DE (1) | DE2611249A1 (en) |
| ES (1) | ES446290A1 (en) |
| FR (1) | FR2308609A1 (en) |
| GB (1) | GB1529384A (en) |
| IN (1) | IN142430B (en) |
| IT (1) | IT1058418B (en) |
| MX (1) | MX3250E (en) |
| NL (1) | NL7604153A (en) |
| NO (1) | NO146707C (en) |
| PT (1) | PT64923B (en) |
| RO (1) | RO69673A (en) |
| YU (1) | YU72876A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1523772A (en) * | 1974-07-22 | 1978-09-06 | Standard Oil Co | Oxidation catalysts |
| CA1133505A (en) * | 1977-07-28 | 1982-10-12 | Andrew T. Guttmann | Process for the oxidation of olefins |
| IL55073A (en) * | 1977-07-28 | 1982-01-31 | Standard Oil Co | Catalysts for the oxidation and ammoxidation of olefins |
| JPS5517306A (en) * | 1978-07-20 | 1980-02-06 | Standard Oil Co | Olefin oxidation using catalyst containing various promoter elements |
| DE3125061C2 (en) * | 1981-06-26 | 1984-03-15 | Degussa Ag, 6000 Frankfurt | Process for the production of acrolein or methacrolein by catalytic oxidation of propylene or isobutylene or tertiary butanol in oxygen-containing gas mixtures |
| DE69033068T2 (en) * | 1989-12-06 | 1999-08-19 | Nippon Catalytic Chem Ind | Process for the production of methacrolein and methacrylic acid |
| JPH0784400B2 (en) * | 1990-04-03 | 1995-09-13 | 株式会社日本触媒 | Process for producing unsaturated aldehyde and unsaturated acid |
| KR940002982B1 (en) * | 1990-06-06 | 1994-04-09 | 미쯔이도오아쯔가가꾸 가부시기가이샤 | Method for preparing acrolein or methacrolein |
| DE4023239A1 (en) * | 1990-07-21 | 1992-01-23 | Basf Ag | METHOD FOR CATALYTIC GAS PHASE OXIDATION OF PROPEN OR ISO-BUTEN TO ACROLEIN OR METHACROLEIN |
| KR950004031B1 (en) * | 1991-02-27 | 1995-04-22 | 미쓰이도오아쓰가가꾸 가부시끼가이샤 | Method for preparing mettacrolein and method for preparing a catalyst for use in the preparation of methacrolein |
| DE4132263A1 (en) * | 1991-09-27 | 1993-04-01 | Basf Ag | METHOD FOR CATALYTIC GAS PHASE OXIDATION FROM ACROLEIN TO ACRYLIC ACID |
| DE4431957A1 (en) * | 1994-09-08 | 1995-03-16 | Basf Ag | Process for the catalytic gas-phase oxidation of propene to acrolein |
| JP3943311B2 (en) | 2000-05-19 | 2007-07-11 | 株式会社日本触媒 | Process for producing unsaturated aldehyde and unsaturated carboxylic acid |
| JP4867129B2 (en) | 2003-12-15 | 2012-02-01 | 三菱化学株式会社 | Method for producing (meth) acrylic acid or (meth) acrolein |
| JP2005213179A (en) * | 2004-01-29 | 2005-08-11 | Mitsubishi Rayon Co Ltd | Catalyst layer and method for forming the same, fixed bed tubular reactor, method for producing methacrolein or methacrylic acid |
| US20050171365A1 (en) * | 2004-02-03 | 2005-08-04 | Grey Roger A. | Epoxidation process using a mixed catalyst system |
| JP5130562B2 (en) * | 2007-11-06 | 2013-01-30 | 日本化薬株式会社 | Method for producing methacrolein and / or methacrylic acid |
| JP2020093216A (en) * | 2018-12-12 | 2020-06-18 | 株式会社Ihi | Catalyst reaction device |
-
1976
- 1976-02-26 IN IN346/CAL/1976A patent/IN142430B/en unknown
- 1976-02-27 GB GB7799/76A patent/GB1529384A/en not_active Expired
- 1976-03-02 CA CA246,905A patent/CA1065341A/en not_active Expired
- 1976-03-03 MX MX100287U patent/MX3250E/en unknown
- 1976-03-12 IT IT7621175A patent/IT1058418B/en active
- 1976-03-17 DE DE19762611249 patent/DE2611249A1/en not_active Withdrawn
- 1976-03-18 ES ES446290A patent/ES446290A1/en not_active Expired
- 1976-03-19 PT PT64923A patent/PT64923B/en unknown
- 1976-03-19 YU YU00728/76A patent/YU72876A/en unknown
- 1976-03-22 CH CH355076A patent/CH619442A5/en not_active IP Right Cessation
- 1976-03-24 BE BE165496A patent/BE839955A/en unknown
- 1976-04-07 AT AT252676A patent/AT343091B/en not_active IP Right Cessation
- 1976-04-10 RO RO7685580A patent/RO69673A/en unknown
- 1976-04-12 JP JP51041165A patent/JPS51127013A/en active Pending
- 1976-04-15 FR FR7611259A patent/FR2308609A1/en active Granted
- 1976-04-19 DD DD192421A patent/DD124592A5/en unknown
- 1976-04-20 NL NL7604153A patent/NL7604153A/en not_active Application Discontinuation
- 1976-04-20 BR BR2429/76A patent/BR7602429A/en unknown
- 1976-04-20 NO NO761326A patent/NO146707C/en unknown
- 1976-04-21 CS CS762622A patent/CS193541B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1529384A (en) | 1978-10-18 |
| PT64923B (en) | 1977-08-24 |
| BE839955A (en) | 1976-07-16 |
| DE2611249A1 (en) | 1976-11-04 |
| BR7602429A (en) | 1976-10-19 |
| ES446290A1 (en) | 1977-06-16 |
| RO69673A (en) | 1981-08-17 |
| AT343091B (en) | 1978-05-10 |
| NO146707B (en) | 1982-08-16 |
| PT64923A (en) | 1976-04-01 |
| NL7604153A (en) | 1976-10-25 |
| DD124592A5 (en) | 1977-03-02 |
| MX3250E (en) | 1980-08-06 |
| ATA252676A (en) | 1977-09-15 |
| CS193541B2 (en) | 1979-10-31 |
| CH619442A5 (en) | 1980-09-30 |
| IN142430B (en) | 1977-07-09 |
| JPS51127013A (en) | 1976-11-05 |
| NO761326L (en) | 1976-10-22 |
| IT1058418B (en) | 1982-04-10 |
| FR2308609A1 (en) | 1976-11-19 |
| FR2308609B1 (en) | 1980-10-03 |
| YU72876A (en) | 1982-05-31 |
| NO146707C (en) | 1982-11-24 |
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