WO2006083098A1 - Method of producing unsaturated fatty acid - Google Patents
Method of producing unsaturated fatty acid Download PDFInfo
- Publication number
- WO2006083098A1 WO2006083098A1 PCT/KR2006/000343 KR2006000343W WO2006083098A1 WO 2006083098 A1 WO2006083098 A1 WO 2006083098A1 KR 2006000343 W KR2006000343 W KR 2006000343W WO 2006083098 A1 WO2006083098 A1 WO 2006083098A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- inactive material
- catalyst
- hot spot
- reaction
- unsaturated fatty
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 33
- 235000021122 unsaturated fatty acids Nutrition 0.000 title claims abstract description 18
- 150000004670 unsaturated fatty acids Chemical class 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 19
- 239000002253 acid Substances 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 14
- 150000007513 acids Chemical class 0.000 description 12
- 238000012856 packing Methods 0.000 description 11
- 239000012808 vapor phase Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000020169 heat generation Effects 0.000 description 8
- 239000012495 reaction gas Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- -1 (meth) acrolein Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B27/00—Bundling particular articles presenting special problems using string, wire, or narrow tape or band; Baling fibrous material, e.g. peat, not otherwise provided for
- B65B27/08—Bundling paper sheets, envelopes, bags, newspapers, or other thin flat articles
- B65B27/083—Storage receptacles therefor
-
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J8/067—Heating or cooling the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65F—GATHERING OR REMOVAL OF DOMESTIC OR LIKE REFUSE
- B65F1/00—Refuse receptacles; Accessories therefor
- B65F1/02—Refuse receptacles; Accessories therefor without removable inserts
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65F—GATHERING OR REMOVAL OF DOMESTIC OR LIKE REFUSE
- B65F2240/00—Types of refuse collected
- B65F2240/156—Paper
Definitions
- the catalyst used in the second step is a catalyst comprising an oxide and/or a composite oxide based on Mo-V, which oxidizes (meth) acrolein-containing mixed gas produced in the first step, particularly (meth) acrolein, to form (meth) acrylic acid as a main product .
- Such methods include a method for' v packing a catalytic bed by controlling the volume of catalyst in such a manner that the volume gradually decreases from the inlet to the outlet (Japanese Laid-Open Patent No . Hei9- 241209) ; a method for packing a catalytic bed by controlling the volume of catalyst particle in such a manner that the volume gradually decreases from the inlet to the outlet; a method for preparing acrylic acid by multistage-packing with catalysts having different activities; a method of dividing inside of a reaction tube into a plurality of reaction zones and packing each catalyst therein; a method for packing a catalytic bed by controlling the activity of catalyst in such a manner that the activity gradually increases from the inlet to the outlet (Japanese Laid-Open Patent No .
- the temperature at the hot spot of a reactor is controlled by the inactive material layer inserted into the hot spot, in such a manner that the temperature of the hot spot is equal to or lower than
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical 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
Disclosed is a method for producing unsaturated fatty acids from unsaturated aldehydes by means of fixed-bed catalytic partial oxidation in a shell-and-tube reactor, characterized in that the reactor includes a reaction zone for producing unsaturated fatty acids, the reaction zone having an inactive material layer inserted into a position where a hot spot is to be generated in a reaction tube. A fixed-bed shell-and-tube reactor for use in the above method is also disclosed. According to the present invention, at least one layer of inactive material is packed at the point of a hot spot to control the hot spot temperature efficiently, thereby increasing the lifetime of a catalyst and producing unsaturated fatty acids with high yield.
Description
METHOD FOR PRODUCING UNSATURATED UNSATURATED FATTY ACID
Technical Field
The present invention relates to a method for producing unsaturated acids from unsaturated aldehydes by means of fixed-bed catalytic partial oxidation in a shell- and-tube heat exchange type reactor, as well as to a fixed- bed shell-and-tube heat exchange type reactor used in the above method.
Background Art
A process for producing unsaturated aldehydes and then unsaturated acids from olefins is a typical example of catalytic vapor phase oxidation. To perform the partial oxidation of olefins, a multimetal oxide containing molybdenum and bismuth or vanadium or a mixture thereof is used as a catalyst . Typically, the partial oxidation of olefins may be exemplified by a process for producing (meth) acrolein and then (meth) acrylic acid by oxidizing propylene or isobutylene, a process for producing phthalic anhydride by oxidizing naphthalene or ortho-xylene or a process for producing maleic anhydride by partially oxidizing benzene, butylene or butadiene. Generally, propylene or isobutylene is subjected to two-step catalytic vapor phase partial oxidation to form (meth) acrylic acid as a final product . More particularly, in the first step, propylene or isobutylene is oxidized by oxygen, diluted inert gas, water vapor and an optional amount of catalyst to form (meth) acrolein as a main product . In the second step, (meth) acrolein obtained from the preceding step is oxidized by oxygen, diluted inert gas,
water vapor and an optional amount of catalyst to form (meth) acrylic acid. The catalyst used in the first step is a catalyst comprising an oxide and/or a composite oxide based on Mo-Bi, which oxidizes propylene or isobutylene to form (meth) acrolein as a main product . Additionally, a part of (meth) acrolein is further oxidized on the same catalyst to form (meth) acrylic acid partially . The catalyst used in the second step is a catalyst comprising an oxide and/or a composite oxide based on Mo-V, which oxidizes (meth) acrolein-containing mixed gas produced in the first step, particularly (meth) acrolein, to form (meth) acrylic acid as a main product .
Reactors for carrying out the above process are realized in such a manner that each of the above two steps are implemented in one system or in two different systems (see US Patent No. 4 , 256, 783) .
Generally, (meth) acrylic acid is reacted with alcohol, to form (meth) acrylate, which is used for paints, fiber formula, coating agent of paper . Especially, a high purity of acrylic acid is used as a raw material for a highly hygroscopic resin, and a demand thereof is recently increasing rapidly.
In general, catalytic vapor phase oxidation is implemented as follows . At least one catalyst in the form of granules is packed into reaction tubes, feed gas is supplied to a reactor through the reaction tubes and the feed gas is in contact with the catalyst in the reaction tubes to perform vapor phase oxidation. Reaction heat generated during the reaction is removed by heat transfer with a heat transfer medium, wherein the temperature of the heat transfer medium is maintained at a predetermined temperature . Particularly, the heat transfer medium for heat exchange is
provided on the outer surface of the catalytic tubes to perform heat transfer . A reaction product mixture containing a desired product is collected via a duct and then sent to a purification step. Generally, catalytic vapor phase oxidation is a highly exothermic reaction. Therefore, it is very important to control the reaction temperature in a specific range and to downsize hot spots in the reaction zone .
Vapor phase partial oxidation for producing unsaturated acids from unsaturated aldehydes is an exothermic reaction. Therefore, it has a problem in that a hot spot (a point whose temperature is abnormally high) is generated in the reactor . Such hot spots show a relatively high temperature compared to other parts of the reactor . Accordingly, in hot spots, complete oxidation proceeds rather than partial oxidation, thereby increasing byproducts such as COx and decreasing the yield of unsaturated acids . Additionally, excessive heat generated in a hot spot causes migration or sublimation of molybdenum that is a main element of the catalyst, resulting in deposition of molybdenum in a catalytic layer and pressure drop in the catalytic layer, degradation of catalytic activity and in shortening of the lifetime of the catalyst . Therefore, yield of unsaturated acid decreases . Generally, various methods are known in order to control the excessive heat at a hot spot in a catalytic reaction accompanied with heat generation. Such methods include a method for reducing the amount of feed gas to decrease the space velocity and a method of using a reaction tube having a relatively small inner diameter . However, when the space velocity decreases, it is not possible to obtain high productivity in an industrial scale . When the inner
diameter of a reaction tube decreases, it is difficult to manufacture the reactor . Moreover, in the latter case, there are disadvantages of economically unfavorable high cost needed for manufacturing the reactor, and increased time and labor needed for packing a catalyst . For these reasons, there has been a continuous need for and research into a method for producing unsaturated aldehydes and/or unsaturated fatty acids with high yield and high productivity by using a catalyst stably for a long time, while avoiding the above problems according to the known methods .
For example, Such methods include a method for'vpacking a catalytic bed by controlling the volume of catalyst in such a manner that the volume gradually decreases from the inlet to the outlet (Japanese Laid-Open Patent No . Hei9- 241209) ; a method for packing a catalytic bed by controlling the volume of catalyst particle in such a manner that the volume gradually decreases from the inlet to the outlet; a method for preparing acrylic acid by multistage-packing with catalysts having different activities; a method of dividing inside of a reaction tube into a plurality of reaction zones and packing each catalyst therein; a method for packing a catalytic bed by controlling the activity of catalyst in such a manner that the activity gradually increases from the inlet to the outlet (Japanese Laid-Open Patent No . 2000- 336060) ; a method for packing a catalytic bed by controlling the amount of catalyst supported on carrier in such a manner that the activity gradually increases from the inlet to the outlet (US No. 2000-336060) ; a method for packing a catalytic bed wherein a first reaction zone most adjacent to the inlet is packed with the catalyst having higher activity than that of the second reaction zone adjacent thereto and then the
catalytic bed from second reaction zone is packed by controlling the activity of catalyst in such a manner that the activity gradually increases from the inlet to the outlet (Japanese Laid-Open Patent No . 2001-112617 ) . However, the above mentioned methods for minimizing degradation of catalyst and suppressing side reactions by decreasing the temperatures of hot spots are not fully effective to solve the above described problems .
Therefore, there is a continuous need for a method for minimizing degradation of catalyst and side reactions caused by extreme heat generation at a hot spot generated during the catalytic reaction .
Brief Description of the Drawings FIG. 1 is a schematic view showing the structure of a reactor according to Comparative Example 2 and Example 2, including catalytic layers and an inactive material layer packed therein .
FIG. 2 is a graph showing the temperature profile of a catalyst bed at 270°C in a reaction zone for producing unsaturated acids from unsaturated aldehydes .
Disclosure of the Invention
It is an object of the present invention to minimize sublimation and/or migration of molybdenum that is a main element of the catalyst, pressure-drop in catalytic layer and degradation of catalytic activity, all of which occur at a hot spot, and to increase the lifetime of catalyst . In order to achieve the object, the present invention provides a method for producing unsaturated fatty acids with high yield in a stable manner for a long time, the method including estimating the position of a hot spot in a
reaction tube and packing an inactive material layer into the hot spot to reduce heat generation at the hot spot, thereby facilitating heat control and/or to disperse a temperature distribution toward a reaction gas outlet . According to an aspect of the present invention, there is provided a method for producing unsaturated fatty acids (ex. (meth) acrylic acid) from unsaturated aldehydes (ex. (meth) acrolein) by means of fixed-bed catalytic partial oxidation in a shell-and-tube reactor, characterized in that the reactor includes a reaction zone for producing unsaturated acids, the reaction zone having an inactive material layer inserted into a position where a hot spot is to be generated in a reaction tube.
According to another aspect of the present invention, there is provided a shell-and-tube reactor that may be used in a method for producing unsaturated fatty acids from unsaturated acids by means of fixed-bed catalytic partial oxidation, characterized in that the reactor includes a reaction zone for producing unsaturated acids, the reaction zone having an inactive material layer inserted into, a position where a hot spot is to be generated in a reaction tube .
Hereinafter, the present invention will be explained in detail . According to the present invention, an inactive material layer is formed at the position of a hot spot in the reactor so that partial oxidation at the hot spot can be prevented, thereby minimizing heat generation at the hot spot and dispersing the temperature distribution, resulting in minimization of degradation of catalyst and side reactions .
As used herein, the term "hot spot" is referred to as
a point where a peak temperature is generated. For example, a hot spot may be a point where an abnormally high temperature is maintained due to excessive heat generation or heat accumulation, in a catalytic bed in the reaction tube of the reaction zone for producing unsaturated acids from unsaturated aldehydes .
A hot spot is formed by the reaction heat generated during catalytic vapor phase oxidation . The position and size of a hot spot are determined by many factors including a reactant composition, space velocity and temperature of heat transfer medium. Under constant processing conditions, a hot spot has a constant position and size. Therefore, the position of a hot spot can be estimated by using a simulation method, etc . In general, each catalytic layer has at least one hot spot . The hot spot may be generated at the front part of the catalytic bed for the oxidation, enriched with a main reactant (unsaturated aldehydes) and molecular oxygen. In addition, the hot spot may be generated at the vicinity of the border of adjacent catalytic layers having different activities, in the case of a reactor structure packed with two or more catalytic layers .
According to the present invention, the position of a hot spot and the temperature peak size of a hot spot are quantitatively analyzed based on the temperature profile
(see FIG. 2 ) of a catalytic bed in a reaction tube . Then, a predetermined height of an inactive material layer is inserted into the temperature peak position where a hot spot is generated so as to prevent partial oxidation at the hot spot, thereby minimizing heat generation at the hot spot and dispersing a temperature distribution.
The reactors that may be used in the present invention
include a fixed-bed multi-tube reactor and a conical fixed- bed multi-tube reactor . There is no particular limitation on the shape of the reactor . In order to form a catalytic bed needed for carrying out vapor phase partial oxidation, a catalyst is packed in the reaction tube of a reactor, an inactive material is packed at the position of a hot spot, in one layer or two or more layers having different kinds and sizes of inactive material, and then the catalyst is further packed in the reaction tube . In the case of the reaction zone for producing unsaturated acids from unsaturated aldehydes, a catalytic bed may be packed in one layer having uniform activity along the axial direction, or in two or more layers whose catalytic activity gradually increases along the axial direction, if necessary.
Preferably, the catalyst used in the vapor phase partial oxidation for producing unsaturated fatty acids is a metal oxide represented by the following formula 1 :
[ formula 1] MOa Ab Bc Cd De Of wherein Mo is molybdenum;
A is at least one element selected from the group consisting of W and Cr;
B is at least one element selected from the group consisting of P, Te, As, B, Sb, Ce, Pb, Mn, V, Nb, and Te;
C is at least one element selected from the group consisting of Si, Al, Zr, Rh, Cu, Ni, Ti, Ag and Sn;
D is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ta, Ca, Mg, Sr, Ba and MgO; and each of a, b, c, d, e and f represents the atomic ratio of each element, with the proviso that when a=12, b is
a number of between 0.01 and 10 , c is a number of between 0.01 and 10, d is a number of between 0.01 and 10, e is a number of between 0.01 and 10, and f is a number defined depending on the oxidation state of each of the above elements .
The catalyst may be supported on carrier having a cylindrical, a hollow cylindrical or spheral shape, and there is no particular limitation in shape of the carrier . The catalyst having a cylindrical shape preferably has an aspect ratio (the ratio of length to diameter (outer diameter) , i . e . , L/D) of between 1 and 1.3. More preferably, the ratio of L/D equals 1. The catalyst having a cylindrical or spherical shape has an outer diameter of preferably
3 ~10mm, and more preferably 5 ~8mm. The inactive material layer that may be used in the present invention may be formed of an inactive material alone or a mixture of an inactive material with a catalyst . However, when a mixture of an inactive material with a catalyst is used, the activity of the mixture should be lower than that of a catalytic layer in the vicinity of a hot spot . The volume ratio of the inactive material to the catalyst in the inactive material layer is preferably 20- 100%, and more preferably 80-100% .
The inactive material that may be used in the present invention is referred to as material inactive to a reaction for producing unsaturated acids from unsaturated aldehydes such as catalytic oxidation of (meth) acrolein. Such inactive materials include silica, alumina, silica/alumina, zirconium oxide, titanium oxide, mixtures thereof, etc . Although there is no particular limitation in shape of the inactive material, the inactive material may have the shape of a sphere, cylinder, ring, rod, and mass with a
suitable size . If necessary, mixtures of the above shapes may be used .
When the inactive material has the shape of a sphere, cylinder and ring, the diameter is preferably 2-10 mm, and more preferably 5-8 mm. When the inactive material has the shape of a cylinder and ring, the ratio of length to diameter (L/D) is preferably 1-1.3, and more preferably is 1. Preferably, the inactive material has the same or similar shape and/or size as the catalyst . At the point of a hot spot, the inactive material layer is packed to the height of 0.1-1000 mm, preferably to the height of 10-200 mm, in one or more layers, preferably in one or two layers . The position where the inactive material layer is disposed in a reaction tube ranges preferably 1-80% and more preferably 1-60% of the total length of the whole catalytic bed in the reaction zone producing unsaturated acid, when viewed from the reaction gas inlet toward the outlet .
It is preferable that the temperature at the hot spot of a reactor is controlled by the inactive material layer inserted into the hot spot, in such a manner that the temperature of the hot spot is equal to or lower than
(reaction temperature + 45°C ) . Accordingly, it is possible to minimize sublimation of catalytically active components and to inhibit side reactions caused by excessive heat, thereby increasing the lifetime of a catalyst and producing unsaturated fatty acids from unsaturated aldehydes with high yield.
Vapor phase partial oxidation for producing unsaturated acids in a reactor having an inactive layer at the hot spot according to the present invention is suitably carried out at a reaction temperature of 200-450°C,
preferably 265-370°C , under a reaction pressure of 0.1-10 atm, preferably 0.5-3 atm. For example, in order to perform oxidation, a feed gas including 5-10 volume% of a feed compound such as (meth) acrolein, 10-13 volume% of oxygen, 5- 60 volume% of water vapor and 20-80 volume% of an inert gas is introduced onto a catalyst at a space velocity of 500- 5000 hr"1 (STP) .
Mode for Carrying Out the Invention Reference will now be made in detail to the preferred embodiments of the present invention. It is to be understood that the following examples are illustrative only and the present invention is not limited thereto . Preparation Example 1 (Preparation of Catalyst)
2000 ml of distilled water was heated with stirring at 100°C and 246 g of ammonium tungstate, 1000 g of ammonium molybdate and 220 g of ammonium vanadate were dissolved therein to form solution (1) . To 500 ml of distilled water, 228 g of copper nitrate, 49 g of strontium nitrate and 25 g of niobium hydroxide were added and mixed thoroughly to form solution (2) . Solution (1) was mixed with solution (2) , to from a catalyst suspension .
The suspension obtained as described above was treated by a homogenizer for 30 minutes or more, and then 20 - 30 wt% of catalytically active components (to the total weight of the supported catalyst) in the suspension state were coated on each spheral carrier having outer diameter of 4.0 - 8.0 mm using a spray nozzle . The resultant was dried at 120°C and baked at 400°C for 5 hours to form spherical catalysts having outer diameters of 4.5 mm (±0.2) , 5 mm (± 0.2) , 8 mm (±0.2) , respectively.
Herein, the resultant catalytically active component except oxygen had the composition of : Mθi2, W2.0, Nb0.2/ V4.0, CU2.0, Sr .0.5
Comparative Example 1
To a stainless steel reactor having an inner diameter of 1 inch and heated with molten nitrate, alumina/silica as an inactive material was packed to the height of 150 mm, and then the catalyst obtained from Preparation Example 1 and having a size of 5 mm (±0.2 ) was packed to the height of 2600 mm, when viewed from the reaction gas inlet toward the outlet .
Example 1
To a stainless steel reactor having an inner diameter of 1 inch and heated with molten nitrate, alumina/silica as an inactive material was packed to the height of 150 mm, the catalyst obtained from Preparation Example 1 and having a size of 5 mm(±0.2) was packed to the height of 300 mm, alumina/silica as an inactive material was packed to the height of 100 mm at the point of a hot spot, and then the catalyst obtained from Preparation Example 1 and having a size of 5 mm(±0.2) was further packed to the height of 2200 mm, when viewed from the reaction gas inlet toward the outlet . Comparative Example 2
To a stainless steel reactor having an inner diameter of 1 inch and heated with molten nitrate, alumina/silica as an inactive material was packed to the height of 150 mm, the catalyst obtained from Preparation Example 1 and having a size of 8 mm (±0.2 ) was packed to the height of 800 mm, and then the catalyst obtained from Preparation Example 1 and having a size of 5 mm (±0.2 ) was further packed to the height
of 2000 mm, when viewed from the reaction gas inlet toward the outlet .
Example 2
To a stainless steel reactor having an inner diameter of 1 inch and heated with molten nitrate, alumina/silica as an inactive material was packed to the height of 150 mm, the catalyst obtained from Preparation Example 1 and having a size of 8 mm (±0.2 ) was packed to the height of 300 mm, alumina/silica as an inactive material was packed to the height of 100 mm at the point of a hot spot, and then the catalyst obtained from Preparation Example 1 and having a size of 8 mm (±0.2) was further packed to the height of 200 mm, when viewed from the reaction gas inlet toward the outlet . Further, the catalyst obtained from Preparation Example 1 and having a size of 5 mm (±0.2 ) was packed to the height of 100 mm, alumina/silica as an inactive material was packed to the height of 100 mm at the point of a hot spot, and then the catalyst obtained from Preparation Example 1 and having a size of 5 mm (±0.2) was packed to the height of 1800 mm.
Comparative Example 3
To a stainless steel reactor having an inner diameter of 1 inch and heated with molten nitrate, alumina/silica as an inactive material was packed to the height of 150 mm, the catalyst obtained from Preparation Example 1 and having a size of 8 mm (±0.2) was packed to the height of 600 mm, the catalyst obtained from Preparation Example 1 and having a size of 4.5 mm (±0.2 ) was packed to the height of 1000 mm, and then the catalyst obtained from Preparation Example 1 and having a size of 5 mm(±0.2 ) was packed to the height of 1000 mm, when viewed from the reaction gas inlet toward the outlet .
Example 3
To a stainless steel reactor having an inner diameter of 1 inch and heated with molten nitrate, alumina/silica as an inactive material was packed to the height of 150 mm, the catalyst obtained from Preparation Example 1 and having a size of 8 mm(±0.2) was packed to the height of 300 mm, alumina/silica as an inactive material was packed to the height of 100 mm at the point of a hot spot , and then the catalyst obtained from Preparation Example 1 and having a size of 8 mm (±0.2) was further packed to the height of 200 mm, when viewed from the reaction gas inlet toward the outlet . Next, the catalyst obtained from Preparation Example 1 and having a size of 4.5 mm (±0.2) was packed to the height of 100 mm, alumina/silica as an inactive material was packed to the height of 100 mm at the point of a hot spot, and then the catalyst obtained from Preparation Example 1 and having a size of 4.5 mm (±0.2 ) was packed to the height of 800 mm. Further, alumina/silica as an inactive material was packed to the height of 100 mm at the point of a hot spot, and then the catalyst obtained from Preparation Example 1 and having a size of 5 mm (±0.2) was packed to the height of 900 mm.
Comparative Example 4
The same catalyst, inactive material and packing heights as Comparative Example 3 were used to provide a reactor, except that a stainless steel fixed-bed conical multi-tube reactor was used instead of the stainless steel reactor having an inner diameter of 1 inch.
Example 4
The same catalyst, inactive material and packing heights as Example 3 were used to provide a reactor, except that a stainless steel fixed-bed conical multi-tube reactor was used instead of the stainless steel reactor having an
inner diameter of 1 inch .
Experimental Example : Catalytic Activity Test The reactors packed with catalysts according to the above Examples and Comparative Examples were used to perform oxidation of acrolein, thereby producing acrylic acid. The oxidation was carried out by introducing a feed gas containing 7 volume% of acrolein, 5.6 volume% of oxygen, 15 volume% of water vapor and 72.4 volume% of inert nitrogen onto the catalyst at the reaction temperature of 265-300°C, under the reaction pressure of 1-3 atm, at the space velocity of 500-2000 hr"1 (STP) .
The results obtained from the above Examples and Comparative Examples are shown in the following Table 1.
In Table 1, the reactant (acrolein) conversion ratio, selectivity and yield are calculated based on the following mathematical formulae 1 and 2. [mathematical formula 1] acrolein conversion ratio (% ) = [moles of reacted acrolein /moles of supplied acrolein ] X 100 [mathematical formula 2 ] yield (%) of acrylic acid = [moles of produced acrylic acid/moles of supplied acrolein] X 100 [Table 1]
Ex. 3 98.67 316 86.84
Comp . Ex. 4 99.40 327 86.85
Ex . 4 99.43 318 87.32
As can be seen from Table 1, reactors of Examples 1-4 including at least one layer of inactive material formed at the point of a hot spot in the catalytic reaction zone according to the present invention can provide excellent acrolein conversion ratio and yield of a desired product of acrylic acid as well as a lower temperature in the point of heat generation .
Industrial Applicability
As can be seen from the foregoing, the present invention provides a method for producing unsaturated fatty- acids from unsaturated aldehydes such as (meth) acrolein, by- means of fixed-bed catalytic vapor phase partial oxidation with molecular oxygen or molecular oxygen-containing gas in a shell-and-tube heat exchange type reactor . According to the present invention, it is possible to minimize the heat generation in hot spots, to disperse a temperature distribution toward an outlet, and thus to produce unsaturated fatty acids stably with high yield for a long time, by virtue of at least one layer of inactive material inserted into a position where a hot spot is to be generated in a reaction tube.
While this invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiment and the drawings . On the contrary, it is intended to cover various
modifications and variations within the spirit and scope of the appended claims .
Claims
1. A method for producing unsaturated fatty acids from unsaturated aldehydes by means of fixed-bed catalytic partial oxidation in a she11-and-tube reactor, characterized in that the reactor includes a reaction zone for producing unsaturated fatty acids, the reaction zone having an inactive material layer inserted into a position where a hot spot is to be generated in a reaction tube .
2. The method according to claim 1, wherein the catalyst for producing unsaturated fatty acids from unsaturated aldehydes is a metal oxide catalyst represented by the following formula 1 :
[ formula 1 ] Moa Ab Bc Cd De Of wherein Mo is molybdenum;
A is at least one element selected from the group consisting of W and Cr;
B is at least one element selected from the group consisting of P, Te, As, B, Sb, Ce, Pb, Mn, V, Nb, and Te;
C is at least one element selected from the group consisting of Si, Al, Zr, Rh, Cu, Ni, Ti, Ag and Sn;
D is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ta, Ca, Mg, Sr, Ba and MgO; and each of a, b, c, d, e and f represents the atomic ratio of each element, with the proviso that when a=12, b is a number of between 0.01 and 10, c is a number of between 0.01 and 10, d is a number of between 0.01 and 10, e is a number of between 0.01 and 10 , and f is a number defined depending on the oxidation state of each of the above elements .
3. The method according to claim 1, which is for producing (meth) acrylic acid from (meth) acrolein .
4. The method according to claim 1, wherein the inactive material layer is formed of an inactive material alone or a mixture of an inactive material with a catalyst .
5. The method according to claim 4 , wherein the inactive material is present in the inactive material layer in a ratio of between 20% and 100% based on the volume of the catalyst .
6. The method according to claim 1 , wherein the inactive material layer is packed to a height of between 0.1 mm and 1000 mm.
7. The method according to claim 4 , wherein the inactive material takes a spherical, cylindrical or ring shape and has a diameter of between 2 mm and 10 mm.
8. The method according to claim 1, wherein the temperature of the hot spot is controlled in such a manner that it is equal to or lower than (reaction temperature + 45°C ) .
9. The method according to claim 1 , wherein the inactive material has the same size, shape or size and shape as the catalyst .
10. A shell-and-tube reactor that may be used in a method for producing unsaturated fatty acids from unsaturated aldehydes by means of fixed-bed catalytic partial oxidation, characterized in that the reactor includes a reaction zone for producing unsaturated fatty acids, the reaction zone having an inactive material layer inserted into a position where a hot spot is to be generated in a reaction tube .
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006800030180A CN101107212B (en) | 2005-02-01 | 2006-02-01 | Method of producing unsaturated fatty acid |
| JP2007554008A JP4850851B2 (en) | 2005-02-01 | 2006-02-01 | Process for producing unsaturated fatty acids |
| EP06715796A EP1846352A4 (en) | 2005-02-01 | 2006-02-01 | Method of producing unsaturated fatty acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2005-0009128 | 2005-02-01 | ||
| KR1020050009128A KR100850857B1 (en) | 2005-02-01 | 2005-02-01 | Method of producing unsaturated fatty acid |
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|---|---|
| WO2006083098A1 true WO2006083098A1 (en) | 2006-08-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2006/000343 WO2006083098A1 (en) | 2005-02-01 | 2006-02-01 | Method of producing unsaturated fatty acid |
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| US (1) | US7365228B2 (en) |
| EP (1) | EP1846352A4 (en) |
| JP (1) | JP4850851B2 (en) |
| KR (1) | KR100850857B1 (en) |
| CN (1) | CN101107212B (en) |
| TW (1) | TWI341305B (en) |
| WO (1) | WO2006083098A1 (en) |
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| WO2012113427A1 (en) * | 2011-02-21 | 2012-08-30 | Lurgi Gmbh | Multi-tube reactor having a structured packing |
| EP3045446A4 (en) * | 2014-04-30 | 2017-01-18 | Mitsubishi Rayon Co., Ltd. | Method for producing (meth)acrylic acid |
| CN109126454A (en) * | 2017-06-27 | 2019-01-04 | 中国石油化工股份有限公司 | A kind of safety-type catalysis oxidation VOCs improvement reactor of temperature control |
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| KR100868454B1 (en) * | 2005-07-08 | 2008-11-11 | 주식회사 엘지화학 | Method of producing unsaturated acid in fixed-bed catalytic partial oxidation reactor with high efficiency |
| WO2009091212A2 (en) * | 2008-01-17 | 2009-07-23 | Lg Chem, Ltd. | Catalyst system, oxidation reactor containing the same, and preparation method for acrolein and acrylic acid using the same |
| JP5314983B2 (en) * | 2008-09-26 | 2013-10-16 | 日本化薬株式会社 | Method for producing methacrylic acid |
| KR101257411B1 (en) | 2009-10-09 | 2013-04-23 | 주식회사 엘지화학 | Method for production of (meth)acrylic acid |
| CN103228356B (en) | 2010-12-03 | 2015-09-23 | 株式会社日本触媒 | Unsaturated carboxylic acid catalyst for preparing and use the preparation method of unsaturated carboxylic acid of this catalyst |
| KR101609984B1 (en) * | 2014-07-09 | 2016-04-06 | 주식회사 엘지화학 | High performance poly-oxometalate catalyst and method for producing the same |
| KR101960919B1 (en) * | 2015-08-11 | 2019-03-22 | 주식회사 엘지화학 | High performance poly-oxometalate catalyst and method for producing the same |
| CA2904477A1 (en) * | 2015-09-14 | 2017-03-14 | Nova Chemicals Corporation | Heat dissipating diluent in fixed bed reactors |
| CN109304157A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | The catalyst of prepared by acrolein oxidation acrylic acid |
| WO2020223048A1 (en) | 2019-05-02 | 2020-11-05 | Dow Global Technologies Llc | Process for aldehyde byproduct reduction in acrylic acid production using highly active and selective catalysts |
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| TW200639150A (en) | 2006-11-16 |
| TWI341305B (en) | 2011-05-01 |
| KR100850857B1 (en) | 2008-08-06 |
| CN101107212A (en) | 2008-01-16 |
| CN101107212B (en) | 2011-09-14 |
| JP2008528683A (en) | 2008-07-31 |
| EP1846352A4 (en) | 2010-06-02 |
| EP1846352A1 (en) | 2007-10-24 |
| US20060211883A1 (en) | 2006-09-21 |
| JP4850851B2 (en) | 2012-01-11 |
| KR20060088292A (en) | 2006-08-04 |
| US7365228B2 (en) | 2008-04-29 |
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