JP5590382B2 - Process for producing unsaturated aldehyde and / or unsaturated carboxylic acid - Google Patents
Process for producing unsaturated aldehyde and / or unsaturated carboxylic acid Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 14
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims 4
- 239000003054 catalyst Substances 0.000 claims description 79
- 239000007789 gas Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000002994 raw material Substances 0.000 claims description 63
- 239000011261 inert gas Substances 0.000 claims description 29
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 18
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 17
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- 150000001299 aldehydes Chemical class 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 150000001735 carboxylic acids Chemical class 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 238000007796 conventional method Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、固定床管型反応器を用いて、プロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルのいずれか１種以上を固体酸化触媒の存在下で気相接触酸化して、（メタ）アクロレイン等の不飽和アルデヒドや、（メタ）アクリル酸等の不飽和カルボン酸を製造する方法に関するものである。 In the present invention, using a fixed bed tubular reactor, one or more of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether is subjected to gas phase catalytic oxidation in the presence of a solid oxidation catalyst, The present invention relates to a method for producing an unsaturated aldehyde such as (meth) acrolein and an unsaturated carboxylic acid such as (meth) acrylic acid.
プロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテル等を気相接触酸化して、（メタ）アクロレイン等の不飽和アルデヒドや、（メタ）アクリル酸等の不飽和カルボン酸を製造するために使用する触媒に関しては、数多くの提案がなされている。これら提案は、主として触媒を構成する元素およびその比率に関するものである。 In order to produce unsaturated aldehydes such as (meth) acrolein and unsaturated carboxylic acids such as (meth) acrylic acid by gas phase catalytic oxidation of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether Many proposals have been made regarding the catalyst to be used. These proposals mainly relate to the elements constituting the catalyst and their ratios.
気相接触酸化は発熱反応であるため、固定床反応器を用いた反応においては、触媒が充填された部分で蓄熱が発生しやすい。特に、この蓄熱で局所的に生じる高温帯域は、ホットスポットと呼ばれている。 Since gas phase catalytic oxidation is an exothermic reaction, in a reaction using a fixed bed reactor, heat storage is likely to occur in a portion filled with a catalyst. In particular, the high temperature zone locally generated by this heat storage is called a hot spot.
このホットスポットの温度が高くなりすぎると、その部分での過度の酸化反応によって、目的生成物の収率が低下することがある。
また、過剰な発熱によって、触媒による反応が促進され、それによりさらに発熱するという悪循環が発生した場合には、触媒が燃焼し、失活してしまうこともある。
If the temperature of the hot spot becomes too high, the yield of the target product may be reduced due to excessive oxidation reaction at that portion.
In addition, when a vicious cycle in which the reaction by the catalyst is promoted due to excessive heat generation and further heat is generated, the catalyst may burn and be deactivated.
ホットスポットにおける過度の発熱を抑制する方法としては、原料の濃度や原料ガスの線速度を下げるなどの措置や、あるいは反応温度を下げる等による、反応負荷の低減が一般的であるが、これらの方法は、目的生成物の生産量の低下をもたらすものである。 As a method for suppressing excessive heat generation at the hot spot, reduction of the reaction load by measures such as reducing the concentration of the raw material or the linear velocity of the raw material gas or reducing the reaction temperature is common. The method results in a reduction in the yield of the target product.
このように不飽和アルデヒドや不飽和カルボン酸の製造において、ホットスポットの温度抑制は重要な課題であり、ホットスポットの存在が、反応条件上の大きな制約となっているのが現状である。 Thus, in the production of unsaturated aldehydes and unsaturated carboxylic acids, temperature control of hot spots is an important issue, and the current situation is that the presence of hot spots is a major restriction on reaction conditions.
したがって、ホットスポットの温度抑制は、（メタ）アクロレイン等の不飽和アルデヒドや、（メタ）アクリル酸等の不飽和カルボン酸を工業的に高収率で製造する上で非常に重要である。 Therefore, temperature control of the hot spot is very important in industrially producing unsaturated aldehydes such as (meth) acrolein and unsaturated carboxylic acids such as (meth) acrylic acid in a high yield.
ホットスポットの温度抑制方法としては、これまでに種々の提案がなされている。
例えば特許文献１には、触媒を充填した固定床多管型反応器を用いて、プロピレン、イソブチレン等のオレフィンを分子状酸素含有ガスにより気相接触酸化して、不飽和アルデヒド及び不飽和カルボン酸を製造する場合において、反応器内の管軸方向に設けられた複数の反応帯に、活性の異なる複数種の触媒を原料ガスの入口から出口に向かって活性が大きくなるように充填することが記載されている。
Various proposals have been made so far for hot spot temperature suppression methods.
For example, Patent Document 1 discloses that an aldehyde such as propylene and isobutylene is vapor-phase catalytically oxidized with a molecular oxygen-containing gas using a fixed-bed multitubular reactor packed with a catalyst to produce an unsaturated aldehyde and an unsaturated carboxylic acid. In the case of producing a catalyst, it is possible to fill a plurality of reaction zones provided in the direction of the tube axis in the reactor with a plurality of types of catalysts having different activities so that the activity increases from the inlet to the outlet of the raw material gas. Have been described.
また、特許文献２には、固定床多管型反応器に孔径を制御した触媒を充填することで、反応負荷が触媒層の一部で局部的に高くなる状況を緩和させ、触媒層全体でほぼ均一化させることが記載されている。 Patent Document 2 describes that by filling a fixed-bed multitubular reactor with a catalyst having a controlled pore size, the situation in which the reaction load is locally increased in a part of the catalyst layer is alleviated. It is described that it is almost uniform.
また、特許文献３には、固定床多管型反応器における各反応管の内部を管軸方向に分割することにより複数個の反応帯を設け、この各反応帯に触媒の真密度に対する触媒の見掛け密度の比Ｒ（触媒の見掛け密度／触媒の真密度）が異なる触媒をそれぞれ充填することで、ホットスポットに位置する触媒の劣化を抑制させる方法が記載されている。 In Patent Document 3, a plurality of reaction zones are provided by dividing the inside of each reaction tube in a fixed bed multi-tube reactor in the axial direction of the catalyst. A method is described in which deterioration of the catalyst located at the hot spot is suppressed by filling each of the catalysts having different apparent density ratios R (apparent density of catalyst / true density of catalyst).
また、特許文献４には、触媒として、内径Ｄ２の開口部を備えた孔部を有する外径Ｄ１の粒状触媒を用いるとともに、固定床多管型反応器における各反応管の内部を管軸方向に分割することにより複数個の反応帯を設け、この各反応帯の少なくとも２つに、Ｄ２の異なる前記触媒をそれぞれ充填することで、ホットスポットがどこに発生するかによらず、高い収率を維持しながら長期にわたって反応を継続することができることが記載されている。 Further, in Patent Document 4, a granular catalyst having an outer diameter D1 having a hole having an opening having an inner diameter D2 is used as a catalyst, and the inside of each reaction tube in a fixed bed multitubular reactor is arranged in the axial direction. A plurality of reaction zones are provided by dividing the catalyst into two, and at least two of the reaction zones are filled with the catalyst having different D2, respectively, so that a high yield can be obtained regardless of where hot spots are generated. It is described that the reaction can be continued for a long time while maintaining.
しかし、特許文献１〜４に記載された方法においては、ホットスポットの温度抑制の効果はあるものの、例えば、気相接触酸化反応の開始直後の不安定な時期に発生しやすい、ホットスポットでの急激な温度上昇に対しては、必ずしも効果が充分ではなかった。 However, in the methods described in Patent Documents 1 to 4, although there is an effect of suppressing the temperature of the hot spot, for example, it is likely to occur at an unstable time immediately after the start of the gas phase catalytic oxidation reaction. The effect was not always sufficient for a rapid temperature rise.
本発明は、気相接触酸化反応によって、不飽和アルデヒド及び／又は不飽和カルボン酸を連続的に製造する場合において、ホットスポットの温度を充分に抑制することを目的とする。 An object of the present invention is to sufficiently suppress the temperature of a hot spot when an unsaturated aldehyde and / or an unsaturated carboxylic acid is continuously produced by a gas phase catalytic oxidation reaction.
本発明は、固体酸化触媒が充填され、熱媒浴を備えた固定床管型反応器の触媒層に、プロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルのいずれか１種以上と、分子状酸素とを少なくとも含有する原料ガスを供給し、気相接触酸化反応によって、不飽和アルデヒド及び／又は不飽和カルボン酸を連続的に製造する方法において、該反応器中の熱媒浴の温度とこれと隣接する該触媒層との温度差が、あらかじめ設定された上限値を超えた時に、不活性ガスを該原料ガスの一部として該触媒層に供給し又は増量し、該原料ガスの供給量を一時的に１容量％以上増加させて該温度差を小さくさせ、該温度差が該上限値を下回った後に、該原料ガスの組成を該不活性ガス増量前に戻す、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である。
The present invention comprises a catalyst bed of a fixed bed tubular reactor filled with a solid oxidation catalyst and equipped with a heat medium bath, and at least one of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether; In the method for continuously producing an unsaturated aldehyde and / or an unsaturated carboxylic acid by supplying a raw material gas containing at least molecular oxygen and performing a gas phase catalytic oxidation reaction, the temperature of the heating medium bath in the reactor When the temperature difference between the catalyst layer and the adjacent catalyst layer exceeds a preset upper limit value, an inert gas is supplied to the catalyst layer as a part of the source gas, or the amount of the source gas is increased. An unsaturated aldehyde which temporarily increases the supply amount by 1% by volume or more to reduce the temperature difference, and returns the composition of the raw material gas to before the increase of the inert gas after the temperature difference falls below the upper limit value. And / or unsaturated It is a method for producing a carboxylic acid.
本発明の方法により、（メタ）アクロレイン等の不飽和アルデヒド及び／又は（メタ）アクリル酸等の不飽和カルボン酸を連続的に製造する場合において、特にスタートアップを効率的かつ安定的に行うことができるとともに、生産能力を高レベルで維持することができる。 In the case of continuously producing unsaturated aldehydes such as (meth) acrolein and / or unsaturated carboxylic acids such as (meth) acrylic acid by the method of the present invention, it is possible to perform startup particularly efficiently and stably. Production capacity can be maintained at a high level.
本発明において、不飽和アルデヒド及び／又は不飽和カルボン酸を合成する反応は、固定床管型反応器を用いて実施される。固定床管型反応器は特に限定されないが、工業的には、例えば、内径１０〜４０ｍｍ、長さ２０００〜７０００ｍｍの反応管を数千〜数万本有するとともに、熱媒浴を備えた多管式反応器を使用することができる。この熱媒浴で用いられる熱媒は特に限定されないが、例えば、硝酸カリウムおよび亜硝酸ナトリウムを含む塩溶融物が挙げることができる。 In the present invention, the reaction for synthesizing the unsaturated aldehyde and / or unsaturated carboxylic acid is carried out using a fixed bed tubular reactor. The fixed-bed tube reactor is not particularly limited, but industrially, for example, a multi-tube having thousands to tens of thousands of reaction tubes having an inner diameter of 10 to 40 mm and a length of 2000 to 7000 mm and a heating medium bath A type reactor can be used. The heat medium used in the heat medium bath is not particularly limited, and examples thereof include a salt melt containing potassium nitrate and sodium nitrite.
本発明で用いられる固体酸化触媒は、特に限定されるものではないが、例えば、下記の式（１）で表される組成を有する、モリブデンを含む複合酸化物を挙げることができる。 Although the solid oxidation catalyst used by this invention is not specifically limited, For example, the complex oxide containing molybdenum which has a composition represented by following formula (1) can be mentioned.
ＭｏａＢｉｂＦｅｃＭｄＸｅＹｆＺｇＳｉｈＯｉ（１）
（式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｓｉ及びＯはそれぞれモリブデン、ビスマス、鉄、ケイ素及び酸素を示し、Ｍはコバルト及びニッケルからなる群より選ばれた少なくとも１種の元素を示し、Ｘはクロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタル及び亜鉛からなる群より選ばれた少なくとも１種の元素を示し、Ｙはリン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモン及びチタンからなる群より選ばれた少なくとも１種の元素を示し、Ｚはリチウム、ナトリウム、カリウム、ルビジウム、セシウム及びタリウムなる群より選ばれた少なくとも１種の元素を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ及びｉは各元素の原子比を表し、ａ=１２の時ｂ=０．０１〜３、ｃ=０．０１〜５、ｄ=１〜１２、ｅ=０〜８、ｆ=０〜５、ｇ=０．００１〜２、ｈ=０〜２０であり、ｉは前記各成分の原子価を満足するのに必要な酸素原子比である。）
Mo a Bi b Fe c M d X e Y f Z g Si h O i (1)
(In the formula, Mo, Bi, Fe, Si and O represent molybdenum, bismuth, iron, silicon and oxygen, respectively, M represents at least one element selected from the group consisting of cobalt and nickel, and X represents chromium. Represents at least one element selected from the group consisting of lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc, and Y represents phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten , Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium, a, b, c, d, e, f, g, h, and i represent the atomic ratio of each element, and when a = 12, b = 0.01 to 3, c = 0.01 to 5, = 1 to 12, e = 0 to 8, f = 0 to 5, g = 0.001 to 2, h = 0 to 20, and i is an oxygen atom necessary for satisfying the valence of each component. Ratio.)
この式（１）で表される組成を有する触媒を調製する方法は特に限定されず、成分の著しい偏在を伴わない限り、従来からよく知られている種々の方法を用いることができる。
この触媒の調製に用いる原料は特に限定されず、各元素の硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物等を組み合わせて使用することができる。例えばモリブデン原料としてはパラモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、塩化モリブデン等を挙げることができる。
The method for preparing the catalyst having the composition represented by the formula (1) is not particularly limited, and various well-known methods can be used as long as the components are not significantly unevenly distributed.
The raw materials used for the preparation of this catalyst are not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, and the like of each element can be used in combination. For example, examples of the molybdenum raw material include ammonium paramolybdate, molybdenum trioxide, molybdic acid, and molybdenum chloride.
本発明に用いられる触媒は無担体でもよいが、シリカ、アルミナ、シリカ・アルミナ、シリコンカーバイト等の不活性担体に担持させたものであっても良く、これらを混合したしたものであってもよい。 The catalyst used in the present invention may be carrier-free, but it may be supported on an inert carrier such as silica, alumina, silica-alumina, silicon carbide, etc., or a mixture of these. Good.
本発明において、触媒層とは、固定床管型反応器の反応管内において少なくとも触媒が含まれている空間部分を指す。すなわち、触媒だけが充填されている空間だけでなく、触媒が不活性担体等で希釈されている空間部分も触媒層とする。ただし、反応管両端部の何も充填されていない空間部分や不活性担体等だけが充填されている空間部分は、触媒が実質的に含まれないので触媒層には含まない。 In the present invention, the catalyst layer refers to a space portion containing at least the catalyst in the reaction tube of the fixed bed tubular reactor. That is, not only the space filled with only the catalyst but also the space where the catalyst is diluted with an inert carrier or the like is used as the catalyst layer. However, the space portion where nothing is filled at both ends of the reaction tube or the space portion where only the inert carrier is filled is not included in the catalyst layer because the catalyst is substantially not included.
プロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルのいずれか１種以上と、分子状酸素とを少なくとも含有する原料ガスを固体酸化触媒の存在下で気相接触酸化して、（メタ）アクロレイン等の不飽和アルデヒドや（メタ）アクリル酸等の不飽和カルボン酸を製造する場合の反応温度は、通常、２３０〜４５０℃の範囲から選ぶのが好ましい。より好ましくは、２５０〜４００℃の範囲である。 Gas phase catalytic oxidation of a raw material gas containing at least one of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether and molecular oxygen in the presence of a solid oxidation catalyst, (meth) The reaction temperature for producing an unsaturated aldehyde such as acrolein and an unsaturated carboxylic acid such as (meth) acrylic acid is usually preferably selected from the range of 230 to 450 ° C. More preferably, it is the range of 250-400 degreeC.
本発明の実施に際して、原料ガス中のプロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルの濃度は、１〜２０容量％の範囲とするのが好ましい。より好ましくは、３〜９容量％の範囲である。
また、原料ガス中の分子状酸素の酸素源としては空気を用いるのが経済的であるが、必要に応じて純酸素を使用することもできる。
原料ガス中の分子状酸素の濃度は５〜１５容量％の範囲が好ましい。
In the practice of the present invention, the concentration of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether in the raw material gas is preferably in the range of 1 to 20% by volume. More preferably, it is in the range of 3 to 9% by volume.
Moreover, although it is economical to use air as the oxygen source of molecular oxygen in the raw material gas, pure oxygen can also be used if necessary.
The concentration of molecular oxygen in the raw material gas is preferably in the range of 5 to 15% by volume.
原料ガス中の酸素濃度は、プロピレン、イソブチレン、第三級ブタノール及びメチル第三級ブチルエーテルの合計に対するモル比でも規定することができ、０．３〜４の範囲とするのが好ましい。 The oxygen concentration in the raw material gas can also be defined by a molar ratio with respect to the total of propylene, isobutylene, tertiary butanol and methyl tertiary butyl ether, and is preferably in the range of 0.3 to 4.
また、原料ガス中には、必要に応じて、窒素、水蒸気、炭酸ガス等の不活性ガスを含有させることができる。
これら不活性ガスは、原料を希釈し、反応管内の空間速度を最適にすることで高収率に目的生成物を得る目的で使用されるものである。原料ガス中における不活性ガスは、必要に応じて適宜選択することができるが、経済性および汎用性の観点から、窒素を用いるのが好ましい。
また、水蒸気の含有比率を５〜５０容量％とすることによって、より高収率で目的生成物を得ることができる傾向にある。
In addition, the raw material gas can contain an inert gas such as nitrogen, water vapor, or carbon dioxide as required.
These inert gases are used for the purpose of obtaining a target product in a high yield by diluting the raw material and optimizing the space velocity in the reaction tube. The inert gas in the source gas can be appropriately selected as necessary, but nitrogen is preferably used from the viewpoints of economy and versatility.
Moreover, it exists in the tendency which can obtain a target product with a higher yield by making the content rate of water vapor into 5 to 50 volume%.
接触気相酸化反応器を使用する製造プロセスは、通常は、反応生成物の捕集工程を有する。したがって、一般的には、目的の原料ガスの組成を得るために、その捕集工程からの排出ガスを利用する。また、この排出ガスを用いるほかにも、不活性ガスである窒素や水蒸気、もしくはその排出ガスを燃焼した後に得られるガスを利用することもできる。 Manufacturing processes that use catalytic gas phase oxidation reactors typically have a reaction product collection step. Therefore, generally, in order to obtain the composition of the target raw material gas, the exhaust gas from the collection process is used. In addition to using this exhaust gas, it is also possible to use an inert gas such as nitrogen or water vapor, or a gas obtained after burning the exhaust gas.
原料ガス量は、同じ設備でできるだけ大きな製造能力を引き出すことと、触媒をより長期間使用することを前提として、目的生成物の高生産性と触媒の長寿命化が両立できる条件として決定することができる。
本発明における気相接触酸化反応は、通常、常圧から数気圧の範囲で実施することができる。
The amount of raw material gas should be determined as a condition that can achieve both high productivity of the target product and long life of the catalyst on the premise of drawing out as much production capacity as possible with the same equipment and using the catalyst for a longer period of time. Can do.
The gas phase catalytic oxidation reaction in the present invention can usually be carried out in the range of normal pressure to several atmospheres.
一般に、気相接触酸化反応は、被酸化原料と分子状酸素を含有する原料ガスを反応器に供給して目的生成物を生成するが、工業的には以下の３つの段階で反応状態が異なる。すなわち、反応初期のスタートアップ時、定常運転時、及び反応終了のシャットダウン時である。 In general, in the gas phase catalytic oxidation reaction, a raw material gas containing an oxidizable raw material and molecular oxygen is supplied to a reactor to generate a target product, but industrially, the reaction state is different in the following three stages. . That is, during startup at the beginning of the reaction, steady operation, and shutdown at the end of the reaction.
スタートアップ時においては、反応開始直後から定常運転条件の被酸化原料が反応器に供給されるわけではなく、被酸化原料の供給量が少ない状態（以下、反応負荷が低い状態）から被酸化原料の供給量が多い状態（以下、反応負荷が高い状態）へと、段階的に原料ガスの供給を変動させている。反応負荷を低い状態から高い状態へと段階的に上げた後、一定の原料ガス供給条件を維持し、この条件で定常運転が開始される。 At the time of start-up, the oxidized raw material under steady operating conditions is not supplied to the reactor immediately after the start of the reaction, but from the state where the supply amount of the oxidized raw material is low (hereinafter, the reaction load is low), The supply of the source gas is fluctuated step by step to a state where the supply amount is large (hereinafter, the reaction load is high). After gradually increasing the reaction load from a low state to a high state, a constant raw material gas supply condition is maintained, and a steady operation is started under this condition.
定常運転の後、触媒交換や設備のメンテナンス等のために、反応を終了させシャットダウンする時には、供給している被酸化原料の供給を停止するとともに、分子状酸素や不活性ガスの供給を停止する操作を実施する。 When the reaction is terminated and shut down for catalyst replacement, equipment maintenance, etc. after steady operation, the supply of the raw material to be oxidized is stopped and the supply of molecular oxygen and inert gas is stopped. Perform the operation.
本発明は、これら各段階において、ホットスポットの温度上昇が発生した時に用いることができる。 The present invention can be used when a hot spot temperature rise occurs in each of these stages.
ホットスポットでの急激な温度上昇は、上述のように、その部分の触媒活性を低下させる恐れがある。そのため、本発明は、このホットスポットの温度をある上限温度以下に保つように運転する方法で行う。すなわち、反応器中の熱媒浴の温度とこれと隣接する触媒層の温度との差であるΔＴ（触媒層温度−熱媒浴層温度）を測定し、このときのΔＴの最高値が、上限を超えるときに、本発明を実施する。この上限値は、触媒の活性などの性質を勘案して、あらかじめ決めることができる。 As described above, the rapid temperature increase at the hot spot may decrease the catalytic activity of the portion. Therefore, the present invention is performed by a method of operating so that the temperature of this hot spot is kept below a certain upper limit temperature. That is, ΔT (catalyst layer temperature−heat medium bath layer temperature), which is the difference between the temperature of the heat medium bath in the reactor and the temperature of the catalyst layer adjacent thereto, is measured, and the maximum value of ΔT at this time is The invention is carried out when the upper limit is exceeded. This upper limit value can be determined in advance in consideration of properties such as the activity of the catalyst.
反応開始直後のスタートアップ時には、原料ガス組成の変動に伴いホットスポットも変動し易く、特にホットスポットにおいて急激な温度上昇が発生し易い。 At the start-up immediately after the start of the reaction, the hot spot is likely to fluctuate as the raw material gas composition fluctuates, and a rapid temperature rise is likely to occur particularly at the hot spot.
本発明は、このようなスタートアップ時において、特に好適に実施することができる。
すなわち、スタートアップ時の原料ガス組成変更後、ホットスポットの温度を監視し、触媒層中のΔＴの最高値が上限を超えた時に、原料ガス量が１容量％以上増量するように一時的に不活性ガスを供給することで、ホットスポットの温度を充分に抑制し、スタートアップを適切かつ効率的に行うことができる。このとき、原料ガスの増加量を１容量％未満とした場合では、ホットスポットの温度抑制効果が不充分となる傾向にある。
好ましくは５容量％以上であり、より好ましくは１０容量％以上であり、さらに好ましくは、３０容量％以上である。
不活性ガス供給による原料ガスの増加量を上げるほど、ΔＴの抑制効果は高くなるが、不活性ガスの供給が過剰になると、触媒の反応率が下がるため、反応率を維持するためには反応温度を上げる必要があり、触媒寿命的には不利となる傾向にある。したがって、原料ガスの増加量は、５０容量％以下とするのが好ましい。
The present invention can be particularly preferably implemented at such startup.
That is, after changing the raw material gas composition at start-up, the temperature of the hot spot is monitored, and when the maximum value of ΔT in the catalyst layer exceeds the upper limit, the amount of raw material gas is temporarily increased so as to increase by 1% by volume or more. By supplying the active gas, the temperature of the hot spot can be sufficiently suppressed, and start-up can be performed appropriately and efficiently. At this time, when the increase amount of the source gas is less than 1% by volume, the temperature suppression effect of the hot spot tends to be insufficient.
Preferably it is 5 volume% or more, More preferably, it is 10 volume% or more, More preferably, it is 30 volume% or more.
As the amount of increase in the raw material gas by increasing the inert gas increases, the effect of suppressing ΔT increases. However, if the inert gas supply becomes excessive, the reaction rate of the catalyst decreases. It is necessary to increase the temperature, which tends to be disadvantageous in terms of catalyst life. Therefore, the increase amount of the source gas is preferably 50% by volume or less.
触媒層中のΔＴの最高値が上限を超えた時に加える不活性ガスとしては、窒素、水蒸気、炭酸ガス等を挙げることができる。
これら不活性ガスは、上述の通り、原料ガス中にも含有させることができるものであり、必要に応じて適宜選択して使用することができるが、経済性やユーティリティーコストの点から、窒素が好ましい。
Examples of the inert gas added when the maximum value of ΔT in the catalyst layer exceeds the upper limit include nitrogen, water vapor, and carbon dioxide.
As described above, these inert gases can also be contained in the raw material gas, and can be appropriately selected and used as necessary. However, from the viewpoint of economy and utility cost, nitrogen is used. preferable.
不活性ガスの増加に伴うホットスポットの局所温度上昇抑制効果によって、触媒層中のΔＴの最高値が上限を下回って安定した時は、不活性ガスを増量する前の原料ガス組成に戻して運転を行う。このとき、不活性ガスを増量前の量に戻さずに運転を続け、触媒が過度の還元雰囲気にさらされる時間が長期間に渡ると、触媒の活性低下を招き、触媒の寿命に悪影響を与える恐れがある。 When the maximum value of ΔT in the catalyst layer is below the upper limit due to the effect of suppressing the local temperature rise of the hot spot accompanying the increase in the inert gas, the operation is returned to the raw material gas composition before increasing the inert gas. I do. At this time, if the operation is continued without returning the amount of the inert gas to the amount before the increase, and the catalyst is exposed to an excessive reducing atmosphere for a long period of time, the activity of the catalyst is reduced and the life of the catalyst is adversely affected. There is a fear.
不活性ガスの供給量を一時的に増加する期間としては、触媒層中のΔＴの最高値が上限を超えた時から、触媒層中のΔＴの最高値が上限を下回って安定した時までが好ましい。 The period during which the supply amount of the inert gas is temporarily increased is from the time when the maximum value of ΔT in the catalyst layer exceeds the upper limit to the time when the maximum value of ΔT in the catalyst layer falls below the upper limit and becomes stable. preferable.
本発明は定常運転時においても好適に用いることができる。すなわち、定常の原料ガス組成に変更後の定常運転時においても、触媒層中のΔＴの最高値が上限を超えた時に、ホットスポットの局所的な発熱を抑制する手段として定常反応条件ガス組成に対して、不活性ガスの供給量を増加し、全体として１容量％以上の量を増量した原料ガスを一時的に供給することで、ホットスポットの温度を充分に抑制し、定常運転を効率的に行うことができる。
好ましい不活性ガスの種類や原料ガスの好ましい増加量は、スタートアップ時の場合と同様である。
The present invention can be suitably used even during steady operation. That is, even during steady operation after changing to the steady raw material gas composition, when the maximum value of ΔT in the catalyst layer exceeds the upper limit, the steady reaction condition gas composition is used as a means for suppressing local heat generation of the hot spot. On the other hand, by increasing the supply amount of inert gas and temporarily supplying the raw material gas whose amount is increased by 1% by volume or more as a whole, the temperature of the hot spot is sufficiently suppressed, and steady operation is efficient. Can be done.
The kind of preferable inert gas and the preferable increase amount of source gas are the same as those at the time of start-up.
本発明はシャットダウン時においても好適に用いることができる。すなわち、定常運転からシャットダウンの段階に切り替わるタイミングにおいては、原料ガス組成の変動に伴いホットスポットも変動し易く、場合によってはホットスポットの急激な上昇が発生することがある。このような場合において、ホットスポットの温度を監視し、触媒層中のΔＴの最高値が上限を超えた時に、原料ガス量が１容量％以上増量するように一時的に不活性ガスを供給することで、ホットスポットの温度を十分に抑制することができ、シャットダウンを効率的に行うことができる。
好ましい不活性ガスの種類や原料ガスの好ましい増加量は、スタートアップ時の場合と同様である。
The present invention can be suitably used even during shutdown. That is, at the timing of switching from the steady operation to the shutdown stage, the hot spot is likely to fluctuate as the raw material gas composition fluctuates, and in some cases, the hot spot may rise rapidly. In such a case, the temperature of the hot spot is monitored, and when the maximum value of ΔT in the catalyst layer exceeds the upper limit, the inert gas is temporarily supplied so that the amount of the raw material gas is increased by 1% by volume or more. Thus, the temperature of the hot spot can be sufficiently suppressed, and shutdown can be performed efficiently.
The kind of preferable inert gas and the preferable increase amount of source gas are the same as those at the time of start-up.
定常運転時やシャットダウン時においても、不活性ガスの供給量を一時的に増加する期間としては、触媒層中のΔＴの最高値が上限を超えた時から、触媒層中のΔＴの最高値が上限を下回って安定した時までが好ましい。 Even during steady operation or shutdown, the period during which the supply amount of the inert gas is temporarily increased is from the time when the maximum value of ΔT in the catalyst layer exceeds the upper limit to the maximum value of ΔT in the catalyst layer. It is preferable until the time when it is stable below the upper limit.
本発明の方法においては、不活性ガスの供給量が増加することに伴い、原料ガス中の原料ガス中のプロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルの反応率が低下する。これは原料ガス全体の流量が増加することにより、原料ガス中のプロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルが反応しきれないまま触媒層を通過する割合が増加するためである。そのため、不活性ガス供給量が増加し原料ガス全体の流量が増加する前後で、プロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルの反応率が一定となるように反応温度を上げて調節することが好ましい。反応温度は、熱媒浴の温度を変えることによって、調節することができる。 In the method of the present invention, as the supply amount of the inert gas increases, the reaction rate of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether in the raw material gas in the raw material gas decreases. This is because the proportion of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether in the raw material gas that passes through the catalyst layer without being reacted increases as the flow rate of the raw material gas increases. Therefore, the reaction temperature is increased and adjusted so that the reaction rate of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether is constant before and after the inert gas supply amount increases and the flow rate of the entire raw material gas increases. It is preferable to do. The reaction temperature can be adjusted by changing the temperature of the heat medium bath.
不活性ガス量を元の状態に戻す場合においては、プロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルの反応率が一定の状態を保つように反応温度を下げて調節することが好ましい。 When returning the amount of the inert gas to the original state, it is preferable to adjust the reaction temperature by lowering so that the reaction rate of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether is kept constant.
また、本発明の効果はホットスポットの局所的な発熱を抑制するに留まらず、触媒の選択率上昇によって目的生成物の生産量が向上する。すなわち、原料ガスの増加による線速度上昇により、原料ガスの逐次酸化が抑制され、目的生成物の選択率が上昇する。このため本発明は、生産量の低下を伴う原料濃度や原料ガス量を低下する従来の技術と比較して、非常に優れたものである。 In addition, the effect of the present invention is not limited to suppressing local heat generation of the hot spot, and the production amount of the target product is improved by increasing the selectivity of the catalyst. That is, due to the increase in the linear velocity due to the increase in the raw material gas, the sequential oxidation of the raw material gas is suppressed, and the selectivity of the target product increases. For this reason, this invention is very excellent compared with the conventional technique which reduces the raw material density | concentration and raw material gas amount accompanying the fall of a production amount.
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。なお、実施例及び比較例中の「部」は質量部を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these. In addition, "part" in an Example and a comparative example means a mass part.
触媒組成は触媒成分の原料仕込み量から求めた。反応器の熱媒としては硝酸カリウム５０質量％及び亜硝酸ナトリウム５０質量％からなる塩溶融物を用いた。ホットスポットは触媒層のΔＴ（触媒層の温度−熱媒浴シェル部内の温度）により検出した。 The catalyst composition was determined from the raw material charge of the catalyst component. As a heat medium for the reactor, a salt melt composed of 50% by mass of potassium nitrate and 50% by mass of sodium nitrite was used. The hot spot was detected by ΔT of the catalyst layer (temperature of the catalyst layer−temperature in the heat medium bath shell).
触媒を充填する固定床管型反応器は、内径２５．４ｍｍで長さが４５００ｍｍの鋼鉄製の反応管を上部管板と下部管板で１３０００本支持された構造のシェル−チューブ式反応器を用いた。 The fixed bed tubular reactor filled with the catalyst is a shell-tube reactor having a structure in which 13,000 steel reaction tubes having an inner diameter of 25.4 mm and a length of 4500 mm are supported by an upper tube plate and a lower tube plate. Using.
シェル−チューブ式反応器内部の各部の反応管における触媒層温度を満遍なく測定できるように、反応器の断面方向と縦方向で３６箇所に熱電対を分散して配置し、各部の温度を測定した。触媒層内の温度は、反応管の断面において中央に位置するよう熱電対を設置して測定した。また、反応時におけるΔＴの最高値の上限を、触媒の活性から勘案して、５２℃とした。 In order to be able to uniformly measure the catalyst layer temperature in the reaction tube of each part inside the shell-tube reactor, thermocouples were distributed and arranged at 36 locations in the cross-sectional direction and the vertical direction of the reactor, and the temperature of each part was measured. . The temperature in the catalyst layer was measured by installing a thermocouple so as to be located at the center in the cross section of the reaction tube. In addition, the upper limit of the maximum value of ΔT during the reaction was 52 ° C. in consideration of the activity of the catalyst.
不活性ガスを増量する場合は、プロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルの反応率が一定となるように少しずつ不活性ガスを増量し、反応温度を上げて調節した。 When increasing the amount of the inert gas, the amount of the inert gas was gradually increased so that the reaction rate of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether was constant, and the reaction temperature was raised to adjust.
また、不活性ガスを元の状態に戻す場合も同様にプロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルの反応率が一定となるように少しずつ不活性ガスを減量し、反応温度を下げて調節した。 Similarly, when returning the inert gas to its original state, the amount of the inert gas is gradually reduced so that the reaction rate of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether becomes constant, and the reaction temperature is reduced. Adjusted by lowering.
原料ガスおよび反応生成ガスの分析はガスクロマトグラフィーにより実施した。なお、プロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルの反応率と、生成する（メタ）アクロレイン（不飽和アルデヒド）及び（メタ）アクリル酸（不飽和カルボン酸）の選択率は以下のように定義される。 The analysis of the raw material gas and the reaction product gas was performed by gas chromatography. The reaction rate of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether and the selectivity of (meth) acrolein (unsaturated aldehyde) and (meth) acrylic acid (unsaturated carboxylic acid) to be produced are as follows: Is defined as
原料の反応率（％）＝（Ｂ／Ａ）×１００
（メタ）アクロレインの選択率（％）＝（Ｃ／Ｂ）×１００
（メタ）アクリル酸の選択率（％）＝（Ｄ／Ｂ）×１００
ここで、Ａは供給した原料であるプロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルのモル数；Ｂは反応した原料のプロピレン、イソブチレン、第三級ブタノール又はメチル第三級ブチルエーテルのモル数；Ｃは生成した（メタ）アクロレインのモル数；Ｄは生成した（メタ）アクリル酸のモル数をそれぞれ示す。
Raw material reaction rate (%) = (B / A) × 100
Selectivity of (meth) acrolein (%) = (C / B) × 100
Selectivity of (meth) acrylic acid (%) = (D / B) × 100
Here, A is the number of moles of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether which are the supplied raw materials; B is the mole of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether of the reacted raw materials Number: C is the number of moles of (meth) acrolein produced; D is the number of moles of (meth) acrylic acid produced.
［実施例１］
純水１０００部にパラモリブデン酸アンモニウム５００部、パラタングステン酸アンモニウム１２．４部、硝酸カリウム１．４部、三酸化アンチモン２７．５部および三酸化ビスマス４９．５部を加え、加熱攪拌した（Ａ液）。別に、純水１０００部に硝酸第二鉄１１４．４部、硝酸コバルト３７０．８部および硝酸亜鉛２１．１部を順次加え、溶解した（Ｂ液）。Ａ液にＢ液を加え水性スラリーとした後、得られた水性スラリーをスプレー乾燥機を用いて乾燥し、得られた乾燥粉を３００℃で１時間焼成を行い焼成物を得た。このようにして得られた焼成物５００部に純水１６０部およびメチルセルロース２０部を混合し、押出成形して外径５ｍｍ、内径２ｍｍ、平均長さ５ｍｍのリング状の湿式賦形体を得た。この湿式賦形体をマイクロ波および熱風を併用する乾燥方法を用いて乾燥させた後に、さらに焼成処理を行い、触媒を得た。
[Example 1]
To 500 parts of pure water, 500 parts of ammonium paramolybdate, 12.4 parts of ammonium paratungstate, 1.4 parts of potassium nitrate, 27.5 parts of antimony trioxide and 49.5 parts of bismuth trioxide were added and heated and stirred (A liquid). Separately, 114.4 parts of ferric nitrate, 370.8 parts of cobalt nitrate and 21.1 parts of zinc nitrate were sequentially added to 1000 parts of pure water and dissolved (Liquid B). After liquid B was added to liquid A to form an aqueous slurry, the resulting aqueous slurry was dried using a spray dryer, and the resulting dried powder was baked at 300 ° C. for 1 hour to obtain a baked product. In 500 parts of the fired product thus obtained, 160 parts of pure water and 20 parts of methylcellulose were mixed and extruded to obtain a ring-shaped wet shaped article having an outer diameter of 5 mm, an inner diameter of 2 mm, and an average length of 5 mm. The wet shaped body was dried using a drying method using both microwaves and hot air, and then subjected to a calcination treatment to obtain a catalyst.
このようにして得られた触媒の金属元素の組成は、Ｍｏ１２Ｂｉ０．９Ｆｅ１．２Ｃｏ５．４Ｚｎ０．３Ｗ０．２Ｓｂ０．８Ｋ０．０６であった。またこの触媒は、前記各金属原子成分の原子価を満足するのに必要な量の酸素から構成される。 The metal element composition of the catalyst thus obtained was Mo 12 Bi 0.9 Fe 1.2 Co 5.4 Zn 0.3 W 0.2 Sb 0.8 K 0.06 . The catalyst is composed of oxygen in an amount necessary to satisfy the valence of each metal atom component.
前記のシェル−チューブ式反応器の各反応管中の原料ガス入口側に、６２０ｍＬの触媒と１３０ｍＬのアルミナ球（外径５ｍｍ）を混合したものを充填し、出口側に７５０ｍＬの触媒１を充填した。このときの各反応管における触媒層の長さは３００５ｍｍであった。
この触媒に、イソブチレン５容量％、酸素１２容量％、水蒸気１０容量％および窒素７３容量％からなる原料ガスを反応温度（熱媒浴温度）３０９℃、接触時間４．５秒で通じた。反応は常圧流通式で行った。反応開始６０分後に反応生成物を捕集して分析したところ、イソブチレンの反応率９７．６％、メタクロレインの選択率８３．２％、メタクリル酸の選択率３．２％であった。
The raw material gas inlet side in each reaction tube of the shell-tube reactor is filled with 620 mL of catalyst and 130 mL of alumina sphere (outer diameter 5 mm), and 750 mL of catalyst 1 is charged on the outlet side. did. At this time, the length of the catalyst layer in each reaction tube was 3005 mm.
A raw material gas consisting of 5% by volume of isobutylene, 12% by volume of oxygen, 10% by volume of steam and 73% by volume of nitrogen was passed through this catalyst at a reaction temperature (heat medium bath temperature) of 309 ° C. and a contact time of 4.5 seconds. The reaction was carried out under normal pressure flow. When the reaction product was collected and analyzed 60 minutes after the start of the reaction, the reaction rate of isobutylene was 97.6%, the selectivity of methacrolein was 83.2%, and the selectivity of methacrylic acid was 3.2%.
この時、触媒層各部のΔＴを測定したところ、最高値は５２．７℃であった。ΔＴの最高値が上限である５２℃を超えたため、元の原料ガス量に対して１５％増量するように窒素ガスを加えた原料混合ガスをイソブチレン反応率が原料ガス量変更前と一定となるように反応温度３１４℃に変更し、接触時間３．９秒にて１．５時間通過させて反応した。 At this time, when ΔT of each part of the catalyst layer was measured, the maximum value was 52.7 ° C. Since the maximum value of ΔT exceeded the upper limit of 52 ° C., the isobutylene reaction rate of the raw material mixed gas in which nitrogen gas was added to increase by 15% with respect to the original raw material gas amount was the same as before the raw material gas amount change. Thus, the reaction temperature was changed to 314 ° C., and the reaction was allowed to pass for 1.5 hours with a contact time of 3.9 seconds.
このとき、ΔＴの最高値は変更前が５２．７℃だったものが４９．８℃に低下し、ΔＴの最高値の低下幅は２．９℃となった。メタクロレインの選択率８４．８％、メタクリル酸の選択率３．０％であった。 At this time, the maximum value of ΔT decreased from 52.7 ° C. before the change to 49.8 ° C., and the range of decrease in the maximum value of ΔT was 2.9 ° C. The selectivity of methacrolein was 84.8%, and the selectivity of methacrylic acid was 3.0%.
［実施例２］
実施例１において、元の原料ガス量に対して３６％増量するように窒素ガスを加え、イソブチレン反応率が原料ガス量変更前と一定となるように反応温度を３１６℃に変更し、接触時間を３．３秒とした以外は同じ条件で実施した結果、ΔＴの最高値は変更前が５２．７℃だったものが４６．２℃まで低下し、ΔＴの最高値の低下幅は６．５℃となった。メタクロレインの選択率８５．５％、メタクリル酸の選択率２．９％であった。
[Example 2]
In Example 1, nitrogen gas was added so as to increase by 36% with respect to the original raw material gas amount, the reaction temperature was changed to 316 ° C. so that the isobutylene reaction rate was constant before the raw material gas amount was changed, and the contact time As a result of carrying out under the same conditions except for 3.3 seconds, the maximum value of ΔT decreased from 52.7 ° C. before the change to 46.2 ° C., and the decrease range of the maximum value of ΔT was 6. It became 5 degreeC. The selectivity of methacrolein was 85.5%, and the selectivity of methacrylic acid was 2.9%.
［実施例３］
実施例１において、元の原料ガス量に対して１％増量するよう窒素ガスを加え、イソブチレン反応率が原料ガス量変更前と一定となるように反応温度を３１０℃に変更し、接触時間を４．５秒にて１．５時間通過させた以外は同じ条件で実施した結果、ΔＴの最高値は変更前が５２．７℃だったものが５１．５℃まで低下し、ΔＴの最高値の低下幅は１．２℃となった。メタクロレインの選択率８３．６％、メタクリル酸の選択率３．０％であった。
[Example 3]
In Example 1, nitrogen gas was added so as to increase by 1% with respect to the original raw material gas amount, the reaction temperature was changed to 310 ° C. so that the isobutylene reaction rate was constant before the raw material gas amount was changed, and the contact time was changed. As a result of carrying out under the same conditions except for passing 1.5 hours at 4.5 seconds, the maximum value of ΔT decreased from 52.7 ° C before the change to 51.5 ° C, and the maximum value of ΔT The decrease width was 1.2 ° C. The selectivity of methacrolein was 83.6%, and the selectivity of methacrylic acid was 3.0%.
［実施例４］
実施例１において、元の原料ガス量に対して７％増量するように窒素ガスを加え、イソブチレン反応率が原料ガス量変更前と一定となるように反応温度を３１２℃に変更し、接触時間を４．２秒にて１．５時間通過させた以外は同じ条件で実施した結果、ΔＴの最高値は変更前が５２．７℃だったものが４９．９℃まで低下し、ΔＴの最高値の低下幅は２．８℃となった。メタクロレインの選択率８４．０％、メタクリル酸の選択率３．０％であった。
[Example 4]
In Example 1, nitrogen gas was added so as to increase by 7% with respect to the original raw material gas amount, the reaction temperature was changed to 312 ° C. so that the isobutylene reaction rate was constant before the raw material gas amount was changed, and the contact time As a result of carrying out under the same conditions except for passing 1.5 seconds at 4.2 seconds, the maximum value of ΔT decreased from 52.7 ° C before the change to 49.9 ° C, and the maximum ΔT The decrease in value was 2.8 ° C. The selectivity of methacrolein was 84.0% and the selectivity of methacrylic acid was 3.0%.
［比較例１］
実施例１において、元の原料ガス量に対して０．４％増量するように窒素ガスを加え、反応温度３０９℃のままでイソブチレン反応率が原料ガス量変更前と一定となることを確認し、接触時間を４．５秒にて１．５時間通過させた以外は同じ条件で実施した結果、ΔＴの最高値は変更前が５２．７℃だったが５２．６℃とほぼ変わらず、ΔＴの最高値の抑制効果は確認できなかった。メタクロレインの選択率８３．４％、メタクリル酸の選択率３．１％とほぼ同等であり、こちらも効果を確認できなかった。
[Comparative Example 1]
In Example 1, nitrogen gas was added so as to increase by 0.4% with respect to the original raw material gas amount, and it was confirmed that the isobutylene reaction rate remained constant before the raw material gas amount was changed with the reaction temperature remaining at 309 ° C. As a result of carrying out under the same conditions except that the contact time was allowed to pass for 1.5 hours at 4.5 seconds, the maximum value of ΔT was 52.7 ° C. before the change, but was almost unchanged from 52.6 ° C. The inhibitory effect of the maximum value of ΔT could not be confirmed. The selectivity of methacrolein was 83.4%, and the selectivity of methacrylic acid was 3.1%, and the effect could not be confirmed.
［比較例２］
実施例１において、窒素ガスを一切増量せずに反応した以外は同じ条件で、ΔＴを確認しつづけたが、ΔＴは５２．７℃でほぼ変わらずΔＴの最高値の抑制効果がないことを確認した。メタクロレインの選択率８３．２％、メタクリル酸の選択率３．２％とほぼ同等であり、こちらも効果を確認できなかった。
[Comparative Example 2]
In Example 1, ΔT was continuously confirmed under the same conditions except that the reaction was carried out without increasing the amount of nitrogen gas. However, ΔT remained substantially unchanged at 52.7 ° C. and there was no effect of suppressing the maximum value of ΔT. confirmed. The selectivity of methacrolein was almost the same as that of 83.2% and the selectivity of methacrylic acid was 3.2%, and the effect could not be confirmed.
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