TWI403362B - 適用於氧化甲醇成甲醛之觸媒 - Google Patents
適用於氧化甲醇成甲醛之觸媒 Download PDFInfo
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- TWI403362B TWI403362B TW094145442A TW94145442A TWI403362B TW I403362 B TWI403362 B TW I403362B TW 094145442 A TW094145442 A TW 094145442A TW 94145442 A TW94145442 A TW 94145442A TW I403362 B TWI403362 B TW I403362B
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- catalyst
- moo
- mixture
- methanol
- molybdate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 230000003647 oxidation Effects 0.000 title abstract description 6
- 238000007254 oxidation reaction Methods 0.000 title abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 26
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
- 229940010552 ammonium molybdate Drugs 0.000 claims 1
- 235000018660 ammonium molybdate Nutrition 0.000 claims 1
- 239000011609 ammonium molybdate Substances 0.000 claims 1
- 229940036348 bismuth carbonate Drugs 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010908 decantation Methods 0.000 claims 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 239000011363 dried mixture Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000008246 gaseous mixture Substances 0.000 claims 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- RQYSWULBRFINID-UHFFFAOYSA-N [Mo].[Ce] Chemical compound [Mo].[Ce] RQYSWULBRFINID-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 229940032296 ferric chloride Drugs 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000009529 body temperature measurement Methods 0.000 description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000015393 sodium molybdate Nutrition 0.000 description 4
- 239000011684 sodium molybdate Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RCMWGBKVFBTLCW-UHFFFAOYSA-N barium(2+);dioxido(dioxo)molybdenum Chemical compound [Ba+2].[O-][Mo]([O-])(=O)=O RCMWGBKVFBTLCW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- IEVWNXLJUKRPPX-UHFFFAOYSA-N bismuth azane Chemical compound N.[Bi+3] IEVWNXLJUKRPPX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 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
- B01J23/28—Molybdenum
-
- 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
- C07C45/37—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 >C—O—functional groups to >C=O groups
- C07C45/38—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 >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- 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
- B01J23/8871—Rare earth metals or actinides
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Description
本發明係關於適用於氧化甲醇成甲醛之觸媒,關於適用於制備觸媒之方法,及其使用於用於製備甲醛之方法中。
工業上在運用於氧化甲醇成甲醛之各種方法中所使用之觸媒(通常稱為鉬酸鐵,因為Fe2
(MoO4
)3
是主要活性成分之一),包括均勻分布在觸媒的整體內之Fe2
(MoO4
)3
和三氧化鉬(MoO3
)兩者。
新鮮觸媒中,Fe/Mo比通常高於1.5但不高於5;然而,由於失去MoO3
,在氧化期間,使它歷經改變,其主要發生在觸媒床中新鮮反應物的進口處及在熱點溫度區域(反應器內部之最大溫度)中。
失去MoO3
確定觸媒性能的降低。在約長期使用後觸媒性能降低需要汰換觸媒,這是長且昂貴之操作。
除去降低觸媒的性能以外,失去MoO3
致使觸媒床崩潰而因此增加負載損失。
因此,覺得需要能提供恆定性能歷充分長久時間之觸媒。
出人意料之外,現已發現一種觸媒,其能符合上文中所引述之要求且除去Fe2
(MoO4
)3
/MoO3
混合物(下文中稱為”基本觸媒”)其中Mo/Fe原子比高於1.5但不高於5以外,亦包括鈰、鉬和氧的一種化合物(下文中稱為鉬酸鈰)其數量以鈰表示為0.2-10重量%。該基本觸媒較佳具有Fe2
(MoO4
)3
2MoO3
組成,而鉬酸鈰以以鈰表示之自0.2至5重量%數量存在。
鉬酸鈰以鈰的鉬酸塩而添加,其中鈰可能是三價及/或四價。在觸媒之活化期間及/或在使用期間,起始之鉬酸鈰可歷經變換。
在高分辨條件中(使用高信號-雜訊比,40-KV銅管,40微安培,具有Cuk α=1.540 598,5至125的2 θ角的範圍,步進0.01及15秒/步進的收集時間),對於成品觸媒的紀錄之X射線經射圖顯示在相當低鈰濃度(300ppm)時,經射線在晶格距離d=8.44,d=6.69和d=4.79其不出現在不具有鈰之觸媒的經射圖中,及在較高之鈰濃度(17000ppm)時,各線出現在較短之晶格距離且明確在d=4.7,d=4.29,d=3.37,D=3.04和d=2.75各距離而且在濃度是3000ppm時所見到之各線移動至較高之晶格距離,即:d=8.53,d=6.74和=d=4.82。
相對於不含鉬酸鈰之觸媒,添加鉬酸鈰具有顯著降低熱點溫度的效果。因此增加觸媒床的穩定性而因此增加其壽命。其他觸媒性能,例如甲醇之轉化率和對於甲醛之選擇性實際上維持不變。
該觸媒自一種水性懸浮液出發來製備,此水性懸浮液含有根據所熟知之方法所獲得之基本觸媒,舉例而言例如自與一可溶性鉬酸塩,例如一種鹼金屬及/或銨的鉬酸塩之溶液中沉澱(懸浮液1)及自經由趁熱,使三氧化鉬(MoO3
)與碳酸鈰(具有42重量%的鈰),具有Mo/Ce莫耳比是1.5至3,較佳是1.6至2.1的含水混合物起反應所獲得之鉬酸鈰之懸浮液(懸浮液2)中沉澱直至CO2
生成停止。
作為替代,懸浮液2可經由使用1.5的Mo/Ce比,混合一種鹼金屬及/或銨的鉬酸塩與一種可溶性三價鈰塩的溶液的懸浮液並用水洗滌該產生之懸浮一直至不需要之離子(NH4 +
,Na+
等)消失而獲得。
該鉬酸鈰亦可經由一種鈰塩和種鉬酸塩再水溶液中起反應而製備並以四價鈰酸塩形式添加至基本觸媒中。
然後將懸浮液1和2混合在一起並將最後產物經由噴霧乾燥來乾燥以使獲得適合於形成粒之一種粉末,通常該(顆)粒成具有一等孔之圓柱體或圓柱體的形式,具有三葉片之橫剖面,在葉片上具有等孔,其具有平行於顆粒的軸之軸或具有其他形狀。該科立具有通常2至7毫米的高度。
然後將顆粒經由在450°至600℃之溫度下,較佳自480°至580℃,在氧化大氣(空氣)中燬燒予以活化。
燬燒通常持續四小時或更多小時。
最後觸媒具有1-7m2
/g的比表面積(BET),較佳3-6m2
/g。
亦可能,但並非是較佳方法之一,均勻混合三價及/或四價鈰鉬酸塩的粉末與基本觸媒的粉末或漿體。
現已發現,且此是根據本發明觸媒的一另外觀點,即:可能便利地使用此等觸媒,尤其具有3-6m2
/g的比表面積者來形成該層的觸媒床其中已達到熱點溫度。該層的觸媒床與新鮮反應物呈接觸。使用此層容許顯著降低觸媒床中之熱點溫度。
氧化甲醇係根據所熟之方法來實施。
氣體混合物包括濃度自6至10體積%之甲醇及濃度自9自13體積%之氧,其餘是惰性氣體(例如氮)。
該反應器是屬於束-管型,反應熱由循環在管外部之一種冷卻液體移除。
此等氣體的線速度是自1至2Nm/sec;浴溫室自250至320°。
將氣體混合物較佳在自120至160℃之溫度下餵入反應器中。
示出下列實施以舉例說明本發明但並非限制本發明的範圍實施。
使用於甲醇氧化成為甲醛之觸媒試驗之實驗工廠由浸沒入熔塩浴中之管式反應器所構成。該反應器是1950毫米長並具有20.4毫米的內直徑。將該觸媒置放在反應器的中央部位中以便保證最大等溫性。
供應氣體自反應器的頂部引入。空氣和氮經由質量流量計量而甲醇藉一恆流汞計量並首先送至蒸發器。
至反應器出口之液流及在清洗塔後之氣體由氣相接析來分析。
試劑:418.6克,碳酸鈰(Ce=42%)271.0克,三氧化鉬
將必需之去礦物質水(大致4升)及三氧化鉬負載入具有有效機械攪拌,溫度量測和控制系統,氣體進口和出口管之大致10升容量之反應器中。在攪拌下加熱實施直至70℃之溫度;於歷經大致60分鐘,添加碳酸鈰並繼續攪拌和加熱歷大致5小時。形成一種濃且容積大之黃色沉澱物。所獲得之鉬酸鈰的數量足夠製備大致58.6仟克之含大致0.3%鈰的觸媒。
試劑:2.5仟克碳酸鈰(Ce=42%)1.62仟克三氧化鉬
將必需之去礦物質水(大致12升)連同二氧化鈰負載入配置有效機械攪拌,溫度量測和控制系統,氣體進口和出口管之大致20升容量之反應器中。在攪拌下加熱實施直至70℃之溫度;於歷經大致60分鐘,添加碳酸鈰並繼續攪拌和加熱歷大致5小時。形成一種濃且容積大黃色沉澱物。產生之鉬酸鈰的數量足夠製備大致61仟克之含大致1.7%鈰的觸媒。
試劑:23.8仟克二氧化鉬40.0仟克鉬酸鈉二水化合物35.2仟克氯化鐵六水合物
將大致1m3
的去礦物質水,三氧化鉬和鉬酸鈉負載入配有一機械攪拌器、一溫度量測和控制系統之大致2.5m3
容量中。實施加熱至60℃直到固體完全溶解為止。
於歷經90分鐘,添加分開製備之氯化鐵溶液(大致0.5m3
),保持反應溫度恆定在60℃。
一旦終止添加氯化鐵,繼續攪拌歷10分鐘,使用去礦物質水,使整體增至2m3
的容積,停止攪拌並容許冷卻直至達到室溫為止。
傾析所沉澱之固體後,使上澄液透明液體溢流,然後將固體在一織物過濾器上過濾,並用去礦物質水洗滌以使移除存在之氯化物。將產生之濾餅傾入一適當槽中,經由機械攪拌轉變成為漿體。
然後將該漿體餵入至一噴霧乾燥器,將它轉化成為乾粉末。在潤滑後,將產生之粉末轉化成為具有多圓筒型狀之粒片。在50℃下燃燒該粒片歷4小時導致形成該使用於甲醇成甲醛之觸媒。
試劑:23.8仟克三氧化鉬40.0仟克鉬酸鈉二水化合物35.2仟克氯化鐵六水化合物
將大致1.0m3
的去礦物質水,三氧化鉬和鉬酸鈉負載入配有一機械攪拌器,並具有溫度量測和控制系統之大致2.5m3
容量的容器中。實施加熱直至60℃之溫度直到固體粒子完全溶解為止。
於歷經90分鐘,添加分開製備之氯化鐵溶液(大致0.5m3
),保持反應溫度恆定在60℃。
一旦終止添加氯化鐵,繼續攪拌歷10分鐘,使用去礦物質水,使整體增至2m3
的容積,停止攪拌並容許冷卻直至達到室溫為止。
傾析所沉澱之固體後,使上澄液液體溢流,然後將固體餾份在一織物過濾器上過濾,並用去礦物質水洗滌以使移除存在之氯化物。將產生之濾餅傾入一適當槽中並經由機械攪拌轉變成為漿體。添加產生之漿體連因根據實例1所製備之鉬酸鈰的懸浮液。在強力攪拌歷至少30分鐘後,將產生之懸浮液餵入一噴霧乾燥器而獲得乾粉末。在潤滑後,將產生之粉末轉或成為具有三葉面之橫剖面之圓柱形粒片並在葉片上具有穿孔。在500℃下煅燒該粒片歷4小時導致形成含有成鉬酸鈰行程之0.3重量%鈰(自化學分析)之觸媒。
試劑:23.8仟克三氧化鉬40.0仟克鉬酸鈉二水化合物35.2仟克氯化鐵六水化合物
得大致1m3
的去礦物質水,三氧化鉬和鉬酸鈉負載入配有一機械攪拌器,溫度量測和控制系統之大致2m3
容量的容器中。實施加熱直至60℃之溫度直到獲得固體粒子之完全溶解為止,附以隨後形成二鉬酸鈉。
於歷經90分鐘的一段時間,添加分開製備之氯化鐵溶液(大致0.5m3
),保持反應溫度恆定在60℃。一旦終止添加氯化鐵,繼續攪拌歷10分鐘,使用去礦物質水,使整體增至20m3
的容積,停止攪拌,並容許冷卻至室溫。
傾析所沉澱之固體後,使上澄液透明液體溢流,然後將固體在一織物過濾器上過濾並用去礦物質水洗滌以使移除存在之氯化物。將產生之濾餅傾入一適當槽中並經由機械攪拌轉變成為漿體。
產生之漿體和根據實例2所製備之鉬酸鈰的懸浮液同時添加。
將兩產物經由強力攪拌均勻混合力至少30分鐘,然後餵入一噴霧乾燥器,其容許獲得一種乾粉末。
在潤滑後,將產生之粉末轉化成為實例3中所製備之該形成的三葉片粒片。
在500℃下燬燒該粒片歷四小時導致形成觸媒,其含有呈鉬酸鈰形式之大致1.56重量%的鈰(自化學分析)。
重複比較實例1的製備,唯一不同是連同三氧化鉬和鉬酸鈉,負載入418.6仟克的碳酸鈰及相當數量(271克)的三氧化鉬。
煅燒後,存在於粉末中之鈰僅是20%的存在於起使鈰化合物質中之鈰。
使用由兩層所構成之一觸媒床:400mm的陶瓷環之上層及700mm的觸媒之下層。
總進口氣流量是1765Nl/小時。進口處混合物的O2
含量是95%。
經由使用比較實施1的觸媒之試驗結果示於下表中:
當在9%甲醇含量下作時,該觸媒快速降解,而因此中斷該試驗,為了評估觸媒降解,在6%甲醇含量時重複工作。
使用實例3的觸媒,試驗的結果示於下表中:
經由使用實例4的觸媒,試驗的結果示於下表中:
Claims (14)
- 一種適用於氧化甲醇成甲醛之觸媒,其包括下列混合物:式Fe2 (MoO4 )3 /MoO3 ,其中Mo/Fe原子比範圍為自1.5至5;及一種三或四價鈰之鉬酸鹽,其含量以鈰表示為自0.1至10重量%,該鉬酸鹽係以一分離相存在,其顯示x射線繞射圖中不會存在於不含鉬酸鈰之觸媒的繞射線。
- 如申請專利範圍第1項之觸媒,其中該鉬酸鹽係以鈰表示為自0.2至5重量%之量存在。
- 如申請專利範圍第1或2項之觸媒,其中該觸媒混合物具有Fe2 (MoO4 )3 2MoO3 組成。
- 如申請專利範圍第1至3項中任一項之觸媒,具有自1至7m2 /g的表面積。
- 如申請專利範圍第4項之觸媒,其中該表面積是2-6m2 /g。
- 如申請專利範圍第4項之觸媒,其中該表面積是3-5 m2 /g。
- 如申請專利範圍第6項之觸媒,該觸媒呈具有一穿孔之圓筒型顆粒的形式或具有一個三葉片型截面之圓筒型顆粒形式,其在葉片上有一穿孔,及孔之軸係平行於顆粒之軸。
- 如申請專利範圍第7項之觸媒,其中該顆粒具有自2至7毫米的高度。
- 一種多層觸媒床,其中與新鮮試劑氣體的混合物接觸之層係由表面積為自3至6 m2 /g如申請專利範圍第1至3項的任一項之觸媒所形成。
- 一種用於製備具有如申請專利範圍第1至8項中任一項所示特性之觸媒之方法,包括下列步驟:a)使一種自與鹼金屬或銨的鉬酸鹽溶液相混合之可溶性鐵塩溶液沉澱出來混合物Fe2 (MoO4 )3 /MoO3 (其Mo/Fe原子比是自1.5至5)所獲得之懸浮液與趁熱經由三氧化鉬和三價鈰的碳酸塩(其Mo/Fe原子比是自1.5至2.1)起反應直至CO2 生成停止所獲得之水性懸浮液混合;b)在與三氧化鉬和碳酸鈰的反應產生之懸浮液混合前,稀釋、傾析、過濾及洗滌,其後經由攪拌轉化成漿體;c)使已乾之混合物或其糊成形,成為顆粒的形式及d)在自450至600℃溫度下煅燒該顆粒。
- 如申請專利範圍第10項之方法,其中該煅燒係在自480至580℃之溫度下實施。
- 一種適用於氧化甲醇成甲醛的方法,其中特濃度是6至10體積%之甲醇與濃度是自9至13體積%之氧而其餘是惰性氣體的氣態混合物使用1-2Nm/s的線速度餵供入束-管型反應器中,其中館內部之觸媒是如申請專利範圍第1至8項中任一項之觸媒且線環管外部之浴溫為自250至320℃。
- 如申請專利範圍第12項之方法,其中與新鮮試劑氣體相接觸之觸媒層係由如申請專利範圍第9項之觸媒形成。
- 如申請專利範圍第12或13項中之方法,其中該試劑氣 體係在自120至160°之溫度下被填入觸媒床。
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CN107610943A (zh) * | 2017-08-09 | 2018-01-19 | 南昌大学 | 一种钼酸铁石墨烯复合结构超级电容器电极材料的制备方法 |
CN109806881A (zh) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | 一种用于甲醇氧化制甲醛的铁钼催化剂及其制备方法 |
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CN115532274A (zh) * | 2022-10-13 | 2022-12-30 | 北京林业大学 | 一种Z型Fe2(MoO4)3/MoO3异质结可见光催化剂及其制备方法与应用 |
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- 2005-12-15 ES ES05027486.9T patent/ES2436752T3/es active Active
- 2005-12-15 EP EP05027486.9A patent/EP1674155B1/en not_active Not-in-force
- 2005-12-15 PT PT50274869T patent/PT1674155E/pt unknown
- 2005-12-16 US US11/303,300 patent/US7468341B2/en not_active Expired - Fee Related
- 2005-12-19 CA CA002530702A patent/CA2530702A1/en not_active Abandoned
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- 2005-12-20 BR BRPI0505595-4A patent/BRPI0505595B1/pt not_active IP Right Cessation
- 2005-12-20 AR ARP050105355A patent/AR052821A1/es not_active Application Discontinuation
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- 2005-12-21 CN CN2005101338270A patent/CN1792443B/zh not_active Expired - Fee Related
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- 2005-12-22 UA UAA200512384A patent/UA92452C2/ru unknown
- 2005-12-22 KR KR1020050127764A patent/KR101237276B1/ko not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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ITMI20042456A1 (it) | 2005-03-22 |
KR101237276B1 (ko) | 2013-02-27 |
ES2436752T3 (es) | 2014-01-07 |
RU2384365C2 (ru) | 2010-03-20 |
TW200628223A (en) | 2006-08-16 |
PL1674155T3 (pl) | 2014-05-30 |
JP2006175436A (ja) | 2006-07-06 |
US20060135821A1 (en) | 2006-06-22 |
UA92452C2 (ru) | 2010-11-10 |
BRPI0505595B1 (pt) | 2015-07-07 |
RU2005140141A (ru) | 2007-06-27 |
PT1674155E (pt) | 2013-12-02 |
EP1674155B1 (en) | 2013-08-28 |
CN1792443B (zh) | 2012-05-02 |
CN1792443A (zh) | 2006-06-28 |
KR20060072083A (ko) | 2006-06-27 |
BRPI0505595A (pt) | 2006-09-12 |
ZA200510296B (en) | 2007-01-31 |
AR052821A1 (es) | 2007-04-04 |
CA2530702A1 (en) | 2006-06-22 |
US7468341B2 (en) | 2008-12-23 |
JP4944438B2 (ja) | 2012-05-30 |
EP1674155A1 (en) | 2006-06-28 |
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