WO2014189341A1 - 아크롤레인 및 아크릴산 제조용 링 촉매 및 이의 용도 - Google Patents
아크롤레인 및 아크릴산 제조용 링 촉매 및 이의 용도 Download PDFInfo
- Publication number
- WO2014189341A1 WO2014189341A1 PCT/KR2014/004670 KR2014004670W WO2014189341A1 WO 2014189341 A1 WO2014189341 A1 WO 2014189341A1 KR 2014004670 W KR2014004670 W KR 2014004670W WO 2014189341 A1 WO2014189341 A1 WO 2014189341A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- ring catalyst
- acrylic acid
- ring
- producing acrolein
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 187
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 86
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000012784 inorganic fiber Substances 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 238000011049 filling Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- 239000004480 active ingredient Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 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
- 238000001354 calcination Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
-
- 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
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
Definitions
- the present invention relates to ring catalysts for the production of acrolein and acrylic acid and their use.
- a method of gas phase catalytic oxidation of propylene, isobutylene or tertiary butanol with molecular oxygen is used in a multi-tubular fixed bed reactor in which a catalyst charge is present.
- the catalyst layer is limited in thickness, or a supported catalyst in which a catalyst active material is supported on a carrier, or a catalyst shaped into a cylinder or a ring is used.
- Various methods are applied.
- a wider void can be secured than the pellet catalyst, and thus, the surface area of the wider catalytically active component and the improved heat dissipation capacity can be exhibited.
- the ring catalyst has a lower mechanical property than the Pel3 ⁇ 4 catalyst, the ring catalyst is easily damaged by impact in the manufacturing process, the storage process, or the process of layering on the semiungung tube. And dust or pieces generated by the breakage of the ring catalyst increases the pressure of the semi-ungung pipe, especially in the case of a multi-tubular semiungung pipe has a problem of irregular pressure per semi-ungung pipe.
- the ring catalyst has a problem in that the life of the catalyst is limited because the content of the catalytically active component layered in the semi-perforated tube is lower than that of the pellet catalyst.
- the present invention is to provide a ring catalyst for producing acrolein and acrylic acid having improved mechanical properties compared to the previous ring catalyst.
- the present invention is to provide a method for producing acrolein and acrylic acid using the ring catalyst.
- L f is the number average length of the inorganic fiber
- D e is the external diameter of the ring catalyst
- Di is the internal diameter of the ring catalyst.
- the catalyst can satisfy the following relation 2:
- Equation 2 L c is the longitudinal length of the ring catalyst, and D e is the outer diameter of the ring catalyst.
- catalytically active component may be represented by Formula 1 below:
- Mo molybdenum
- Bi bismuth
- A is at least one element selected from the group consisting of Fe, Zn, Mn, Nb and Te
- B is at least one element selected from the group consisting of Co, Rh and Ni
- C is at least one element selected from the group consisting of Na, K, Li, Cs, Ta, Ca, Rb and Mg
- 0 oxygen
- the inorganic fiber may be at least one member selected from the group consisting of glass fibers, silica fibers, alumina fibers, and silica-alumina fibers.
- the inorganic fiber may have a number average length of 2 2 or less and a number average diameter of 2 to 40 /.
- the inorganic fiber may be included in an amount of 2 to 15 parts by weight based on 100 parts by weight of the active ingredient.
- At least one raw material compound selected from the group consisting of propylene, isobutylene and tertiary butanol is provided with a process for producing acrolein and acrylic acid comprising contact gas phase oxidation with molecular oxygen.
- the catalytic gas phase oxidation reaction may be performed in a multi-tubular fixed bed reactor in which the ring catalyst is layered.
- the ring catalyst may satisfy the relational expression 2.
- the ring catalyst is layered in the reactor in at least two layers having different L c / D e , and the L c / D e can decrease gradually in the direction from the inlet side of the raw compound inlet to the product outlet side. have.
- the catalyst for preparing acrolein and acrylic acid has excellent mechanical properties, which enables more uniform layering and minimizes the collapse of the catalyst, and lowers the initial pressure of reaction by securing stable voids, and over a longer period of time. It can be used stably.
- the method for preparing acrolein and acrylic acid according to the present invention enables the provision of more improved production efficiency by using the catalyst.
- FIG. 1 is an enlarged view of a catalyst according to an embodiment of the present invention.
- the inventors of the present invention in the course of repeated studies to improve the above problems, add the inorganic fiber together with the catalytically active component in the production of the ring catalyst, in particular the ratio of the number average length of the wall thickness of the ring catalyst and the inorganic fiber
- the mechanical properties of the catalyst can be significantly improved.
- the catalyst is applied to the production process of acrolein and acrylic acid, it was confirmed that the problem of reducing the effective amount of the catalytically active component by using the ring catalyst can be minimized and improved productivity can be ensured.
- Catalysts for preparing acrolein and acrylic acid are provided that satisfy the following relationship:
- L f is the number average length of the inorganic fiber
- D e is the external diameter of the ring catalyst
- Di is the internal diameter of the ring catalyst.
- the catalyst for producing acrolein and acrylic acid according to the present invention includes a mixture of a catalytically active component and an inorganic fiber, and has a ring shape as shown in FIG.
- the catalytically active component may include conventional components applied to acrolein and a catalyst for producing acrylic acid, and preferably, at least molybdenum (Mo) and bismuth (Bi) are advantageous for securing catalytic activity. . More preferably, the catalytically active component may be represented by the following Chemical Formula 1:
- Mo molybdenum
- Bi bismuth
- A is at least one element selected from the group consisting of Fe, Zn, Mn, Nb and Te
- B is at least one element selected from the group consisting of Co, Rh and Ni
- C is at least one element selected from the group consisting of Na, K, Li, Cs, Ta, Ca, Rb and Mg
- 0 is oxygen;
- the catalytically active component represented by the formula (1) can exhibit excellent catalytic activity in the production of acrolein and acrylic acid, thereby providing improved reaction efficiency.
- the catalyst according to the present invention comprises an inorganic fiber that is uniformly mixed with the catalytically active component.
- the catalyst according to the present invention not only exhibits improved mechanical properties as it contains inorganic fibers, but also exhibits increased reaction properties .
- the exotherm can be dissipated, enabling the suppression of consecutive react ions and the degradation of the catalyst by heat.
- the material of the inorganic fiber is not particularly limited, and those conventional in the art to which the present invention pertains may be applied.
- the inorganic fibers may be at least one member selected from the group consisting of glass fibers, silica fibers, alumina fibers and silica-alumina fibers in order to sufficiently express the aforementioned effects without adversely affecting the catalytic activity. desirable.
- the content of the inorganic fiber included in the catalyst of the present invention can be determined in a range that does not reduce the catalytic activity while the above-described effects due to the addition of the inorganic fiber can be expressed sufficiently.
- the content of the inorganic fiber may be 2 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the catalytically active component.
- the mechanical properties of the ring catalyst may exhibit a significant difference according to the correlation between the number average length of the inorganic fibers and the wall thickness of the ring catalyst.
- the catalyst according to the present invention may satisfy the following relation 1.
- Equation 1 L f is the number average length of the inorganic fiber, D e is the external diameter of the ring catalyst and D,-is the internal diameter of the ring catalyst.
- the catalyst according to the present invention has a number average length (L f) of inorganic fibers included in the catalyst according to the wall thickness [(D e -Di) / 2] of the catalyst. ) Is designed to vary, in particular the ratio [2L f / (D e -Di)] satisfies the above equation (1).
- the [2L f / (D e -Di)] may be 0.1 to 0.19, or 0.12 to 0.19, or 0.12 to 0.18, or 0.12 to 0.16, or 0.14 to 0.16.
- the catalyst according to the present invention may include an inorganic fiber to express the optimum mechanical properties improving effect according to the wall thickness of the catalyst.
- the supporting capacity of the catalytically active component on the inert carrier can be secured to some extent.
- the mechanical properties of the catalyst may be generally reduced, such as a high wear rate of the catalyst and a drop in drop strength.
- the mechanical properties of the catalyst may be somewhat lowered, and the activity of the catalyst may be lowered, which is not preferable.
- the wall thickness ([(D e -Di) / 2]) of the catalyst may be 0.5 kPa or more to secure the basic structural stability of the catalyst, preferably 0.5 to 5.0 mm, more preferably 1.0 to It may be 4.0 mm.
- the number average length (L f ) of the inorganic fiber is 2 kPa or less (non-limiting examples 0.05 to 2mm or 0.1 to 1.5mm, or 0.1 to 1mm) for uniform mixing with the catalytically active component And it can be determined in a range satisfying the relation 1 according to the wall thickness of the catalyst.
- the number average diameter of the inorganic fiber may be 2 or more for the expression of the effect of the addition of the inorganic fiber, preferably 2 to 40 ⁇ , more preferably 4 to 20.
- the catalyst according to the present invention has a shape satisfying the following relation 2:
- L c is the longitudinal length of the ring catalyst and D e is the outer diameter of the ring catalyst.
- the catalyst according to the present invention has a ring shape (ie, a hollow cylinder shape), and the longitudinal length L e of the ring catalyst is inherent in the ring catalyst (eg, For example, it can be determined in the range that can be secured wide pores, semi-heat heat dissipation capacity, etc.), preferably in a range that satisfies the relationship 2 in the relationship with the outer diameter (D e ) of the ring catalyst. .
- the ring catalyst according to the invention may have at least, two types having different L c / D e.
- the ring catalyst is used for reaction in a layered state on a contact gas phase oxidation reaction reactor (eg, a multi-tubular stationary bed reaction reactor) for producing acrolein and acrylic acid, at least two having different L c / D e .
- the catalyst can be used to form a catalyst layer imparted with different layering densities of the catalyst.
- the ring catalyst is 0.2 to 1, or 0.2 to 0.9, or 0.2 to 0.7, or 0.3 to 0.7, or 0.3
- two or more catalysts having a second form having L c / D e of 0.6 to 1.5, or 0.6 to 1.3, or 0.7 to 1.3, or 0.8 to 1.2, or 0.9 to 1.2, or 1 to 1.2. have.
- the laminar density of the catalyst layer in the reaction chamber can be adjusted as necessary by controlling the shape of the ring catalyst.
- the filling method of the ring catalyst will be described in more detail in the description of the production method of acrolein and acrylic acid.
- the catalyst according to the present invention may be prepared by molding a powdery mixture comprising the catalyst active ingredient and inorganic fibers into a ring shape as shown in FIG. At this time, the calcination is advantageous in terms of expression of sufficient catalytic activity to be carried out for 2 to 7 hours in an oxygen atmosphere of 300 to 700 ° C. Meanwhile, according to another embodiment of the present invention,
- a process for producing acrolein and acrylic acid comprising the step of contacting gaseous phase oxidation with molecular oxygen of at least one raw material compound selected from the group consisting of propylene, isobutylene and tertiary butanol. .
- the above-described ring catalyst can be applied to the production of acrolein and acrylic acid can exhibit excellent activity.
- the raw material compound of the production method at least one compound selected from the group consisting of compounds conventional in the art, for example, propylene, isobutylene and tertiary butanol may be used.
- the raw compound may be converted into acrolein and acrylic acid through contact gas phase oxidation reaction with molecular oxygen.
- the catalytic gas phase oxidation reaction may be performed in a multi-tubular fixed bed reactor in which the ring catalyst is layered.
- the multi-tubular fixed-bed reactor may be provided with a shell-and-tube type heat exchanger, and in addition to the conventional structure in the art to which the present invention pertains without particular limitation. Can be.
- the ring catalyst satisfying the above-mentioned relational formula 1 and having excellent mechanical properties is applied, so that the catalyst can be layered uniformly while the collapse of the catalyst can be minimized.
- the above-described catalyst is applied to the manufacturing method, so that the pressure at the initial stage of the reaction can be lowered as much as possible to secure stable voids, and the operation of the stable process can be performed for a longer time.
- the ring catalyst applied to the method for producing acrolein and acrylic acid satisfies the above relationship 2.
- the ring catalyst may be filled in a semi-unggi (each semi-unggi pipe in the case of a multi-tubular fixed bed reactor) with at least two layers having different L c / D e , wherein the L c / D e is It can be stratified to decrease gradually from the source compound inlet side toward the product outlet side.
- ring catalysts can secure a wider void in the reactor (i.e. lower laminar density) than pellet catalysts, resulting in good heat dissipation capacity, whereas the content of catalytically active components present in the reactor is relatively There is a low disadvantage.
- the ring catalyst when the ring catalyst is applied, as the content of the charged active ingredient (ie, the catalytically active ingredient) decreases, the life of the catalyst is shortened, making it difficult to operate the process for a long time and lowering the production efficiency. .
- the above problems can be solved by giving different layering densities by controlling the shape of the ring catalyst filled in the reaction vessel. That is, in the present invention, the ring catalyst is layered in at least two layers having different L c / D e , in particular the L c / D e is in the direction of the product outlet side from the raw material inlet side of the semi-ungunggi Stratified to decrease gradually.
- This imparts a relatively low laminar density to the catalyst layer on the side of the source compound inlet, and a relatively high laminar density in the subsequent sections.
- the production method according to the present invention can secure a reaction activity and a heat dissipation effect at the same time by giving a wide pore at the side of the raw material inlet in which active reaction occurs.
- the content of the active ingredient (catalyst active ingredient) filled in the entire semi-unggi group can be increased. Accordingly, it is possible to compensate for the shortening of the catalyst life due to the reduction of the filled active ingredient, and thus it is possible to operate a stable process for a longer time.
- the L c / D e control range of the ring catalyst according to the section of the half-unggi can be determined in a range in which the catalytic effect can be secured while the above-described effects can be sufficiently expressed.
- the ring catalyst may comprise a first form having an L c / D e of 0.2 to 1, or 0.2 to 0.9, or 0.2 to 0.7, or 0.3 to 0.7, or 0.3 to 0.5; And two or more catalysts having a second form having L c / D e of 0.6 to 1.5, or 0.6 to 1.3, or 0.7 to 1.3, or 0.8 to 1.2, or 1 to 1.2.
- a subsequent layer may be formed of a catalyst layer including a catalyst of the second type, which is L c / D e 7 ⁇ 0.2 to 1.
- the catalyst of the first type and the catalyst of the second type may be Other L c / D e ).
- the length of each catalyst layer is not particularly limited because it may be determined in consideration of reaction efficiency and the like.
- the molar ratio of the raw material compound and oxygen introduced into the reactor may be 1: 0.5 to 1: 3, the reaction may be carried out at 200 to 450 ° C and 0.1 to 10 atm.
- preferred embodiments will be presented to assist in understanding the present invention. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples.
- a first solution was prepared by dissolving about 1000 g of ammonium molybdate while heating about 2500 mr of distilled water to about 90 ° C. in a 5 liter volume glass reactor equipped with a stirrer.
- Example 1 To prepare a suspension.
- the prepared suspension is placed in an electric oven at approximately 13 CTC.
- the mixture was dried for about 24 hours, and then stirred for about 2 hours while grinding it to a particle size of about 130 m or less to obtain a powder.
- Example 1 To prepare a suspension.
- the prepared suspension is placed in an electric oven at approximately 13 CTC.
- the mixture was dried for about 24 hours, and then stirred for about 2 hours while grinding it to a particle size of about 130 m or less to obtain a powder.
- a mixture comprising 5 parts by weight of silica-alumina fiber (number average diameter about 7, number average length (L f ) about 225) with respect to 100 parts by weight of the catalytically active component according to the preparation example was stirred for about 30 minutes.
- the extrusion molded product was calcined for about 5 hours in an oxygen atmosphere of about 500 ° C. to obtain a catalyst.
- the composition ratio of the elements except oxygen of the catalytically active component is Moi2Bi 2 .2Fei. 4 Co5.5 o.4.
- the mixture comprising 5 parts by weight of silica-alumina fiber (number average diameter about 7 zm, number average length (L f ) about 225 m) with respect to 100 parts by weight of the catalytically active component according to the preparation example was stirred for about 30 minutes.
- the extrusion molded product was calcined for about 5 hours in an oxygen atmosphere of about 500 ° C. to obtain a catalyst.
- a mixture comprising silica-alumina fibers (number average diameter about 7 ⁇ , number average length (L f ) about 150 5 parts by weight based on 100 parts by weight of the catalytically active ingredient according to the preparation example was stirred for about 30 minutes.
- the mixture comprising 5 parts by weight of silica-alumina fiber (number average diameter about 7, number average length (L f ) about 180) with respect to 100 parts by weight of the catalytically active component according to the preparation example was stirred for about 30 minutes.
- the mixture was extruded in the form of a ring having an outer diameter (D e ) of about 5 mm, an inner diameter (Di) of about 2 mm, and a longitudinal length (L c ) of about 5.5 mm ((2L f / (D e -Di)).
- ] About 0.12
- L c / De about 1.1).
- the extrusion molded product was calcined for about 5 hours in an oxygen atmosphere of about 500 ° C to obtain a catalyst.
- the extrusion molded product was calcined for about 5 hours in an oxygen atmosphere of about 500 ° C to obtain a catalyst.
- a catalyst was obtained in the same manner as in Example 1 except that no silica-alumina fibers were added. Comparative Example 5
- acrolein and acrylic acid were prepared by vapor phase catalytic oxidation reaction using propylene as a raw material.
- the reaction is a shell-and-tube type heat exchanger equipped with a multi-tube fixed bed reactor (inner diameter of the tube 1 inch; diameter of the shell 350 mm; length of catalyst filling section-catalyst of Example 1 2000mm on the raw material mixed gas inlet side) ,
- a raw material mixed gas (8% by volume propylene, 14% by volume oxygen, 18% by volume water vapor and 60% by volume inert gas) was subjected to a space velocity of 1500 hr— 1 It was carried out under a reaction temperature of about 305 ° C.
- the catalyst according to the embodiments was confirmed to have excellent mechanical properties such as impact strength, wear rate, drop strength, while excellent catalyst activity compared to the catalyst according to the comparative examples .
- the catalyst of Example 1 was charged on the inlet side of the raw material mixing gas and the catalyst of Example 2 was laminated in the subsequent section, the catalytic activity equivalent to that of the case of using the catalyst of Example 2 alone could be ensured. It was found that the mechanical stability of the catalyst layer and the life of the catalyst were more excellent.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015555115A JP2016510258A (ja) | 2013-05-24 | 2014-05-26 | アクロレインおよびアクリル酸製造用環触媒およびその用途 |
EP14800472.4A EP2937140A4 (en) | 2013-05-24 | 2014-05-26 | CYCLIC CATALYST FOR THE PREPARATION OF ACROLEIN AND ACRYLIC ACID, AND USE THEREOF |
CN201480011340.2A CN105026037A (zh) | 2013-05-24 | 2014-05-26 | 用于制备丙烯醛和丙烯酸的环状催化剂及所述催化剂的应用 |
US14/766,590 US20150367329A1 (en) | 2013-05-24 | 2014-05-26 | RING-SHAPED CATALYST FOR PREPARING ACROLEIN AND ACRYLIC ACID, AND USE THEREOF (As Amended) |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2013-0059095 | 2013-05-24 | ||
KR20130059095 | 2013-05-24 | ||
KR1020140062552A KR101554317B1 (ko) | 2013-05-24 | 2014-05-23 | 아크롤레인 및 아크릴산 제조용 링 촉매 및 이의 용도 |
KR10-2014-0062552 | 2014-05-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014189341A1 true WO2014189341A1 (ko) | 2014-11-27 |
Family
ID=52457672
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2014/004670 WO2014189341A1 (ko) | 2013-05-24 | 2014-05-26 | 아크롤레인 및 아크릴산 제조용 링 촉매 및 이의 용도 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20150367329A1 (ko) |
EP (1) | EP2937140A4 (ko) |
JP (2) | JP2016510258A (ko) |
KR (1) | KR101554317B1 (ko) |
CN (2) | CN105026037A (ko) |
WO (1) | WO2014189341A1 (ko) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102297983B1 (ko) * | 2017-05-25 | 2021-09-02 | 주식회사 엘지화학 | (메타)아크롤레인 및/또는 (메타)아크릴산 제조용 촉매 조성물과 이의 제조 방법 |
US20220023837A1 (en) * | 2019-09-30 | 2022-01-27 | Lg Chem, Ltd. | Ammoxidation catalyst for propylene, manufacturing method of the same catalyst, ammoxidation method using the same catalyst |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07185349A (ja) * | 1993-12-28 | 1995-07-25 | Mitsubishi Rayon Co Ltd | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒の製造法 |
KR20020075281A (ko) * | 2001-03-21 | 2002-10-04 | 가부시키가이샤 닛폰 쇼쿠바이 | 불포화 알데히드 및 불포화 카르복실산 제조용 촉매 |
KR20030070105A (ko) * | 2001-01-15 | 2003-08-27 | 바스프 악티엔게젤샤프트 | (메트)아크릴산의 전구체 화합물의 불균일 촉매작용-기상부분 산화 방법 |
JP2005211796A (ja) * | 2004-01-29 | 2005-08-11 | Mitsubishi Chemicals Corp | 均一な強度を有する複合酸化物触媒の製造方法。 |
KR20090079835A (ko) * | 2008-01-17 | 2009-07-22 | 주식회사 엘지화학 | 촉매 시스템, 이를 포함하는 산화 반응기, 및 이를 이용한 아크롤레인 및 아크릴산의 제조방법 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3276984B2 (ja) * | 1992-06-19 | 2002-04-22 | 三菱レイヨン株式会社 | 不飽和アルデヒド及び不飽和カルボン酸合成用担持触媒及びその製造法 |
US5532199A (en) * | 1992-06-19 | 1996-07-02 | Mitsubishi Rayon Co., Ltd. | Carrier-supported catalyst for the synthesis of unsaturated aldehydes and unsaturated carboxylic acids and process for preparing the same |
JP3826413B2 (ja) * | 1995-08-17 | 2006-09-27 | 住友化学株式会社 | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒成形体の製造方法 |
JP2988660B2 (ja) * | 1996-12-12 | 1999-12-13 | 株式会社日本触媒 | メタクロレインおよびメタクリル酸の製造方法 |
WO2000024804A1 (fr) * | 1998-10-23 | 2000-05-04 | Toyo Boseki Kabushiki Kaisha | Catalyseur de polymerisation destine a la production de polyester, polyester et procede de production associe |
MY121878A (en) * | 1999-03-10 | 2006-02-28 | Basf Ag | Method for the catalytic gas-phase oxidation of propene into acrylic acid |
JP3943311B2 (ja) * | 2000-05-19 | 2007-07-11 | 株式会社日本触媒 | 不飽和アルデヒドおよび不飽和カルボン酸の製造方法 |
JP4995373B2 (ja) * | 2001-02-20 | 2012-08-08 | 三菱レイヨン株式会社 | 反応管、触媒の製造方法、不飽和アルデヒドおよび不飽和カルボン酸の製造方法 |
ZA200209470B (en) * | 2001-12-04 | 2003-06-03 | Rohm & Haas | Improved processes for the preparation of olefins, unsaturated carboxylic acids and unsaturated nitriles from alkanes. |
JP2008264766A (ja) | 2007-03-29 | 2008-11-06 | Nippon Shokubai Co Ltd | 酸化物触媒および該触媒を用いたアクロレインまたはアクリル酸の製造方法ならびに当該アクリル酸を用いた吸水性樹脂の製造方法 |
JP5163273B2 (ja) * | 2008-05-16 | 2013-03-13 | 住友化学株式会社 | 不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法 |
EP2617491B1 (en) * | 2010-09-17 | 2020-10-21 | Nippon Shokubai Co., Ltd. | Catalyst for producing unsaturated aldehyde and/or unsaturated carboxylic acid and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid using catalyst |
CN101992093A (zh) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | 高选择性制备不饱和醛和不饱和酸催化剂的制备方法 |
CN102989470B (zh) * | 2011-09-08 | 2014-10-15 | 中国石油天然气股份有限公司 | 一种低碳烯烃氧化制不饱和醛催化剂及其制备方法 |
-
2014
- 2014-05-23 KR KR1020140062552A patent/KR101554317B1/ko active IP Right Grant
- 2014-05-26 US US14/766,590 patent/US20150367329A1/en not_active Abandoned
- 2014-05-26 JP JP2015555115A patent/JP2016510258A/ja not_active Withdrawn
- 2014-05-26 CN CN201480011340.2A patent/CN105026037A/zh active Pending
- 2014-05-26 CN CN201810506882.7A patent/CN108514882A/zh active Pending
- 2014-05-26 WO PCT/KR2014/004670 patent/WO2014189341A1/ko active Application Filing
- 2014-05-26 EP EP14800472.4A patent/EP2937140A4/en not_active Withdrawn
-
2016
- 2016-11-30 JP JP2016231908A patent/JP6482518B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07185349A (ja) * | 1993-12-28 | 1995-07-25 | Mitsubishi Rayon Co Ltd | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒の製造法 |
KR20030070105A (ko) * | 2001-01-15 | 2003-08-27 | 바스프 악티엔게젤샤프트 | (메트)아크릴산의 전구체 화합물의 불균일 촉매작용-기상부분 산화 방법 |
KR20020075281A (ko) * | 2001-03-21 | 2002-10-04 | 가부시키가이샤 닛폰 쇼쿠바이 | 불포화 알데히드 및 불포화 카르복실산 제조용 촉매 |
JP2005211796A (ja) * | 2004-01-29 | 2005-08-11 | Mitsubishi Chemicals Corp | 均一な強度を有する複合酸化物触媒の製造方法。 |
KR20090079835A (ko) * | 2008-01-17 | 2009-07-22 | 주식회사 엘지화학 | 촉매 시스템, 이를 포함하는 산화 반응기, 및 이를 이용한 아크롤레인 및 아크릴산의 제조방법 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2937140A4 * |
Also Published As
Publication number | Publication date |
---|---|
JP6482518B2 (ja) | 2019-03-13 |
EP2937140A1 (en) | 2015-10-28 |
EP2937140A4 (en) | 2016-05-11 |
KR20140138081A (ko) | 2014-12-03 |
JP2016510258A (ja) | 2016-04-07 |
US20150367329A1 (en) | 2015-12-24 |
CN105026037A (zh) | 2015-11-04 |
CN108514882A (zh) | 2018-09-11 |
JP2017080742A (ja) | 2017-05-18 |
KR101554317B1 (ko) | 2015-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2832718B1 (en) | Process for producing acrylic acid using fixed-bed multitubular reactor | |
KR101642163B1 (ko) | 기하학적 촉매 성형체의 제조 방법 | |
JP5628930B2 (ja) | 不飽和アルデヒドおよび/または不飽和カルボン酸製造用触媒および該触媒を用いる不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 | |
JP6407278B2 (ja) | アルケンを気相酸化して不飽和アルデヒド及び/又は不飽和カルボン酸にするための、機械的に安定な中空円筒形触媒成形体 | |
US8399711B2 (en) | Process for preparing (meth)acrolein by heterogeneously catalyzed gas phase partial oxidation | |
US9090577B2 (en) | Catalyst for producing ethylene oxide and method for producing ethylene oxide | |
KR20080086365A (ko) | 불포화 알데히드 및/또는 불포화 카르복실산의 제조법 | |
JP4242597B2 (ja) | 不飽和アルデヒド合成用触媒とその製造方法、およびその触媒を用いた不飽和アルデヒドの製造方法 | |
JP2016539936A (ja) | 不飽和アルデヒド及び/又は不飽和カルボン酸の製造法 | |
JP5945371B2 (ja) | アクロレインおよびアクリル酸製造用触媒とその製造方法 | |
KR100660988B1 (ko) | 불포화 알데히드의 제조방법 | |
JP6482518B2 (ja) | アクロレインおよびアクリル酸製造用環触媒の製造方法および触媒を用いたアクロレインおよびアクリル酸の製造方法 | |
EP2832717B1 (en) | Method for producing acrylic acid and acrolein using fixed-bed multitubular reactor | |
TWI247628B (en) | Production Process for unsaturated aldehyde | |
JP5295815B2 (ja) | メタクロレインおよびメタクリル酸の製造触媒 | |
KR102297983B1 (ko) | (메타)아크롤레인 및/또는 (메타)아크릴산 제조용 촉매 조성물과 이의 제조 방법 | |
WO2007119607A1 (ja) | メタクロレイン及び/又はメタクリル酸の製造法 | |
WO2012008625A1 (ja) | 水素および一酸化炭素の混合ガスの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480011340.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14800472 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014800472 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2015555115 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14766590 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |