TWI462777B - 合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法 - Google Patents
合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法 Download PDFInfo
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- TWI462777B TWI462777B TW098136794A TW98136794A TWI462777B TW I462777 B TWI462777 B TW I462777B TW 098136794 A TW098136794 A TW 098136794A TW 98136794 A TW98136794 A TW 98136794A TW I462777 B TWI462777 B TW I462777B
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- Prior art keywords
- catalyst
- dimethyl ether
- methanol
- temperature
- solid carrier
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 228
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims description 149
- 239000003054 catalyst Substances 0.000 title claims description 130
- 230000002194 synthesizing effect Effects 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 51
- 230000015572 biosynthetic process Effects 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 39
- 238000006297 dehydration reaction Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 230000018044 dehydration Effects 0.000 claims description 29
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000003980 solgel method Methods 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000693 micelle Substances 0.000 claims description 6
- 239000011859 microparticle Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000011943 nanocatalyst Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001879 gelation Methods 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910000951 Aluminide Inorganic materials 0.000 claims description 2
- 238000012993 chemical processing Methods 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 239000000446 fuel Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- -1 ZSM-5 is used Chemical compound 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000005218 dimethyl ethers Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本發明係有關於一種合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,尤指涉及一種採用溶膠凝膠法調變觸媒之晶粒大小、晶型、表面結構及活性中心分布之性質,特別係指兼具甲醇合成及甲醇脫水兩種活性位置之微粒徑之奈米觸媒者。
二甲醚(Dimethyl Ether,DME),分子式為CH3
OCH3
。其物理性質非常類似液化石油氣-丙烷與丁烷,可在常溫-25℃下或常壓6大氣壓下被液化,並可利用現行液化石油氣(Liquified Petroleum Gas,LPG)儲運設備,混入或替代LPG作為家用或商用燃料。由於二甲醚本身具有醚類特有之味道,不像天然氣或LPG需再添加有臭味之添加劑,而燃燒時火焰亦類似甲烷且亮度高。在汽車燃料方面,由於LPG、天然氣及甲醇等燃料之十六烷值均小於10,僅適合用於點燃式發動機,如汽油引擎;而二甲醚十六烷值係大於55,具優良壓縮性,非常適合用於壓燃式發動機,作為柴油之替代燃料。基於二甲醚燃燒時不會產生硫化物(SOx),且氮化物(NOx)與二氧化碳(CO2
)等溫室氣體排放量極低,係一種類似於LPG之液化氣燃料。相較於甲烷、甲醇、乙醇及FT-柴油等替代燃料,從生命週期之溫室氣體排放、能源效率、非化石原料之儲存量、燃料之用途、現有設施之相容性、及經濟性等議題觀之,以二甲醚作為替代燃料之優點有沸點低、氧含量高及高十六烷值等,因此二甲醚可以說是最具有發展潛力之替代燃料者,其應用領域主要包括化學品原料、氯氟碳(Chlorofluorocarbon,CFC)化合物替代品、柴油車替代燃料、家用或商用LPG取代、氣渦輪機或柴油發動機發電、以及燃料電池燃料等。台灣有98%之能源仰賴進口,加上共同參與解決全球暖化問題之國際趨勢,積極推動再生能源與替代能源係當務之急。其中環境電漿合成氣以一步驟法直接生產二甲醚係目前最可行之發展方向,但要有經濟規模之生產,尚待更好之觸媒研發。
二甲醚工業生產方式主要有兩種,如第6圖所示,分別為一步驟法與兩步驟法,其中一步驟法係由合成氣作為進料經一個反應器一步直接合成二甲醚;而該兩步驟法係由合成氣或天然氣等作為進料經一個反應器先合成甲醇後,再以甲醇作為進料經另一個反應器合成二甲醚之製程。目前全球已有工廠在生產二甲醚之國家包含有美國、日本、中國、韓國、伊朗及丹麥等,其中丹麥之二甲醚廠可同時產出甲醇與二甲醚。無論係以上述一步驟法或兩步驟法生產二甲醚,都要先將原料轉化為合成氣,其方式包括有一般採用天然氣經過蒸汽重組反應以產生合成氣,或利用煤、生質材作為原料氣化成合成氣,再進而合成二甲醚;亦或使用環境電漿合成氣則可直接生產二甲醚。目前工業製之二甲醚主要係經由兩步驟法所製造,亦即先由合成氣在銅系觸媒作用下生成甲醇,再利用鋁系、或沸石系觸媒,將甲醇脫水以獲得二甲醚。而最新之一步驟法,則係在合成與脫水觸媒之共同作用下,讓甲醇合成反應與脫水反應在同一個反應器中同時進行,使得甲醇一經生成即被轉化為二甲醚,並能較兩步驟法更能提高二甲醚之轉化率。
以上述一步驟法製造二甲醚而言,由於合成氣合成二甲醚之反應為連續性反應,使得生成之甲醇很快脫水轉化成二甲醚。此反應不僅增加反應驅動力,更突破單純合成甲醇反應中之熱力學平衡限制,使得轉化率較單純合成甲醇時還要高。若比較合成甲醇與合成二甲醚之吉布斯自由能(Gibbs Free Energy),在一般之觸媒活性溫度150~300℃範圍內,合成甲醇之吉布斯自由能為2~18仟焦耳/莫耳(kJ/mol),比合成二甲醚之吉布斯自由能為-10~13kJ/mol為大,因此合成二甲醚反應驅動力增加;當溫度提高到380℃時,合成甲醇與合成二甲醚反應之吉布斯自由能皆相等為24kJ/mol;然而,當溫度提高到380℃以上時,合成甲醇之吉布斯自由能反而比合成二甲醚之吉布斯自由能小,因此合成二甲醚反應驅動力減弱,甚至傾向合成甲醇反應。若從轉化率之觀點考慮,在大約100~400℃範圍內,合成二甲醚之一氧化碳轉化率較合成甲醇之轉化率高,因此,一步法合成二甲醚在理論上較合成甲醇更容易。在一般觸媒活性溫度150~300℃範圍內,溫度對合成二甲醚反應影響明顯,溫度升高一氧化碳平衡轉化率下降較快;在200~400℃時,壓力對反應影響明顯,隨著壓力升高,一氧化碳轉化率很快升高。若考慮反應物成分比例,當進料莫耳比值H2
/CO升高到2時,一氧化碳轉化率不再升高;當H2
/CO升高到3時,一氧化碳轉化率與H2
/CO為2時相同。故,經上述合成氣直接合成二甲醚之熱力學理論分析可知,合成氣直接合成二甲醚反應最理想之反應條件係較低之溫度、較高之壓力與適當之合成氣組成。
合成氣直接合成二甲醚之反應過程包括三個相互關聯之反應,分別為甲醇合成反應、甲醇脫水反應與水煤氣轉移反應,其各別之反應方程式並如下所示:
(1)4H2
+2CO→2CH3
OH(甲醇合成)
(2)2CH3
OH→CH3
OCH3
+H2
O(甲醇脫水)
(3)CO+H2
O→CO2
+H2
(水煤氣轉移)
(4)3CO+3H2
→CH3
OCH3
+CO2
(總反應)
依據合成氣直接合成二甲醚之反應過程,二甲醚合成觸媒至少必須兼具甲醇合成、甲醇脫水與水煤氣轉移等多重功能,即在觸媒設計上必須同時含有這幾種活性中心。而習知技術對於觸媒之製備方法主要分為以機械混合法製備之複合觸媒,及以特定化學合成方法製備之多功能觸媒,其中:以複合觸媒之製備而言,該機械混合法操作簡單,可避免兩種或三種觸媒製備時處理條件之不同與相互干擾等問題,並可隨意調節觸媒之間之比例,使得幾種觸媒之間可能達到一種平衡。故此法適用於各種類型觸媒活性成分之篩選,還可用來進行觸媒反應機制方面之研究。其中以使用之反應器類型直接合成二甲醚觸媒之效能而言:在固定床反應器中使用之觸媒,混合時有乾混法與濕混法。其中乾混法不添加溶劑直接將不同觸媒成分攪拌進行充分之機械混合,此種方法之缺點係壓製成特定形狀後之觸媒機械強度不太高;而該濕混法係在混合攪拌之前加入少量之惰性揮發液體,然後攪拌使得觸媒成為糊狀得以均勻混合,接著烘乾觸媒使液體揮發,該法之好處在於觸媒可以充分地混合均勻,缺點則係液體溶劑不能夠充分地蒸乾,殘留之水等液體成分將影響觸媒之還原效果。
在漿狀床反應器中使用之觸媒,只需將經過簡單攪拌混合之觸媒置入反應器中,其中的攪拌或鼓泡動力會將觸媒均勻懸浮於一定量之惰性介質中,即可達到複合觸媒之充份混合。
按,美國申請第4,423,155號專利案為Chang與Bell較早提出採用銅鋅鋁合成之甲醇觸媒與三氧化鋁(γ-Al2
O3
)組成之複合觸媒。係研究合成氣直接合成二甲醚反應,並指出在250~400℃範圍內,此觸媒可以再生。最近文獻報導較多係利用各種分子篩合成甲醇觸媒與脫水觸媒對合成氣直接合成二甲醚反應進行研究,探討兩種觸媒之製備方法、配比及反應條件對合成二甲醚反應之影響;同時亦利用不同合成甲醇觸媒與HZSM-5分子篩以及經過水熱處理之分子篩組成之複合觸媒,進行觸媒活性研究,發現分子篩酸性之強、弱中心對二甲醚之生成作用不同。在分子篩上只有弱酸性之活性中心(Active Site)及合適之鹼性活性中心才有利於二甲醚之生成。而強酸性之活性中心則將甲醇或二甲醚進一步脫水生成烴類,反而降低反應生成二甲醚之選擇率。
故,此種觸媒係將兩種或三種催化劑研磨,按照一定比例進行機械混合,配製成機械混合式之觸媒。根據上述合成氣直接合成二甲醚之反應方程式(1)、(2)及(3)可知,合成過程中需要三種類型觸媒,包括甲醇合成觸媒、甲醇脫水觸媒與水煤氣轉移觸媒,若忽略水煤氣轉移反應,前兩個反應可以看成係連續反應步驟。在這兩個反應中,甲醇合成觸媒與甲醇脫水觸媒之其中之一效果不好時,將會成為限制整個反應速率之瓶頸步驟。雖然該些複合觸媒可用機械混合單獨具有甲醇合成活性中心及單獨具有甲醇脫水活性中心來製備;然而,根據文獻報導,該些複合觸媒中之活性成分並未被精細地分散好,因此複合觸媒如何產生最好之連續性反應,使得生成之甲醇很快脫水轉化成二甲醚,係目前尚待突破之重要研究課題。
以多功能觸媒之製備而言,係將兩種或兩種以上有效觸媒活性中心,透過特定化學合成方法使其直接緊密生成於載體孔道中。由於不同之有效觸媒活性中心能更緊密地接觸,能減少對流與擴散等質傳之影響,因而能相對地提高整體反應之轉化率與二甲醚之反應選擇率。早期研究者已提出將硝酸銅、硝酸鋅等擔載於三氧化鋁(γ-Al2
O3
),研究不同銅、鋅含量對觸媒性能影響。目前,多功能二甲醚觸媒之製備方法係以共沉澱法與溶膠凝膠法最為有效。然而,一般有關二甲醚合成之文獻報導中之觸媒使用溫度係在250~280℃,高於理論上單純之合成甲醇與甲醇脫水之反應溫度,這表示其使用之觸媒活性較低,兩種活性中心功能未發揮到最佳程度。因此,不只使反應受到熱力學限制,而且一氧化碳轉化對於穩定性不好之銅基觸媒來說,也必將縮短其使用週期。
綜上所述,以合成氣一步法直接製二甲醚係比甲醇脫水二步法製二甲醚具有較高轉化率及低成本優勢。因環境電漿合成氣直接製二甲醚之技術關鍵仍為觸媒,由反應機構可知,合成氣一步法直接製二甲醚觸媒必須具備催化甲醇合成反應與甲醇脫水反應兩種功能。觸媒依其製備法與作用機制,可分為兩類,包括複合觸媒與多功能觸媒。其中複合觸媒係由甲醇合成觸媒與甲醇脫水觸媒機械混合而成,為技術發展初期常使用之觸媒,甲醇合成觸媒為銅基觸媒,脫水劑為具酸性之分子篩與三氧化鋁(γ-Al2
O3
)等,製備過程包括破碎、沉澱、洗滌、過濾、乾燥、造粒及成型等。相關研究顯示,觸媒比例對合成氣轉化率與二甲醚生成速率有顯著影響;此外,相關專利亦指出若於脫水劑中添加適量磷酸鋁以作為甲醇脫水助劑,並與甲醇合成觸媒有效結合,將可延長觸媒使用壽命。然而,複合觸媒之缺點在於製備程序繁雜,所需設備較多,因此觸媒效能亦隨製備條件之不同而改變,無法提高觸媒之低溫活性、選擇性及穩定性等之有效性能。故,一般習用者係無法符合使用者於實際使用時之所需。
本發明之主要目的係在於,克服習知技藝所遭遇之上述問題並提供一種兼具甲醇合成及甲醇脫水兩種活性位置之微粒徑之Cu-Zn-Al觸媒者。
本發明之次要目的係在於,提供一種透過改變組成、凝膠沉澱及後處理條件,俾利調變觸媒之晶粒大小、晶型、表面結構及活性中心分布之性質,從而改善觸媒之性能者。
為達以上之目的,本發明係一種合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,係採用溶膠凝膠法選用適當之溶劑與界面活性劑形成與混合鹽溶液不互溶之有機相,運用成膠後表面張力之變化,使製備過程中生成之膠團粒子迅速轉移至該有機相中,藉以對膠團起隔離作用,透過阻止其再老化與乾燥過程中變大,進而製成微粒徑之奈米觸媒者。
請參閱『第1圖』所示,係本發明之製備流程示意圖。如圖所示:本發明係一種合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,係採用溶膠凝膠法選用適當之溶劑與界面活性劑形成與混合鹽溶液不互溶之有機相,運用成膠後表面張力之變化,使製備過程中生成之膠團粒子迅速轉移至該有機相中,藉以對膠團起隔離作用,透過阻止其再老化與乾燥過程中變大,進而製成微粒徑之奈米觸媒。其至少包含下列步驟:
(A)提供合成觸媒步驟11:提供一含有催化活性成分鹽類之乙醇溶液,其中,該催化活性成分係指提供含有一氧化碳(CO)加氫(H2
)活性中心之銅(Cu)、鋅(Zn)及鋁(Al)、或銅及鋅所組成之活性成分者;
(B)提供脫水觸媒步驟12:提供一含有脫水活性之微孔性固體載體,其中,該含有脫水活性之微孔性固體載體係指提供含有脫水活性中心之分子篩、三氧化鋁(γ-Al2
O3
)或矽鋁化物之固體載體,且該分子篩係為沸石(ZSM-5);
(C)攪拌生成微粒步驟13:將上述含有催化活性成分鹽類之乙醇溶液,與上述固體載體於一溫度介於-5~4℃之間進行充分攪拌,並緩慢逐滴加入一含草酸之乙醇溶液使之混合沉澱,生成與該固體載體緊密結合之草酸鹽微粒;
(D)真空揮發步驟14:將上述緊密結合有草酸鹽微粒之固體載體置於一真空濃縮環境下,以真空揮發方式去除其中乙醇成分;
(E)高溫煅燒步驟15:將上述已去除乙醇成分之固體載體置於高溫爐中,在一溫度介於500±10℃之間進行高溫煅燒,以高溫煅燒方式將其中草酸有機物析出去除;
(F)冷卻步驟16:將經煅燒後之固體載體予以冷卻;
(G)氫氣煅燒還原步驟17:將上述冷卻後之固體載體置於通入有氫氣氣氛之高溫爐中,在一溫度介於400±10℃之間進行高溫煅燒,脫附結合於該固體載體中之氧原子,並還原結合於該固體載體中之金屬觸媒微粒,如銅、鋅、鋁;以及
(H)物理加工步驟18:將上述經過一連串化學加工處理後之固體載體,經壓片、破碎及過篩之物理加工處理,即得一兼具甲醇合成及甲醇脫水兩種活性位置之Cu-Zn-Al觸媒。
藉以上述各步驟,透過改變組成、凝膠沉澱及後處理條件,俾利調變觸媒之晶粒大小、晶型、表面結構及活性中心分布之性質,從而改善觸媒之性能者。
當本發明於運用時,於一較佳實施例中,係採用分子篩,如ZSM-5,與銅、鋅等含有催化活性成分鹽類之乙醇溶液進行充分攪拌,使含有催化活性成分鹽類之乙醇溶液有充分時間擴散滲透至分子篩之微孔道中,之後再緩慢逐滴加入含草酸之乙醇溶液,並於溫度控制在0℃且轉速大於300rpm以上進行充分攪拌,使生成之草酸鹽可控制為草酸鹽微粒,以避免沉澱粒子過大。繼之,先將其置於真空濃縮環境下揮發去除乙醇成分,之後再以高溫500℃進行煅燒處理,藉以將載有CuO及ZnO之分子篩中內含之草酸有機物析出並去除;待其冷卻後,再以高溫400℃之氫氣氣氛下進行煅燒還原處理,藉以脫附去除其中氧原子以還原載於該分子篩中之銅、鋅觸媒微粒。最後,經過物理加工之壓片、破碎及過篩處理後,即獲得以溶膠凝膠製程製得具奈米粒徑之Cu-Zn-ZSM5觸媒。
請參閱『第2圖』所示,係本發明Cu-Zn-Al觸媒之X光繞射(XRD)圖譜示意圖。如圖所示:係為本發明所製得之Cu-Zn-ZSM5觸媒之XRD分析結果,其可分析出經過氫氣煅燒還原處理後之觸媒,其強度(Intensity)較大之活性物種為Cu,證明本製程確實可產生銅。
請參閱『第3圖及第4圖』所示,係分別本發明以合成觸媒對合成氣應用之產物分佈示意圖、及本發明之溫度對產量關係示意圖。如圖所示:係本發明將合成氣以上述自製之Cu-Zn-ZSM5觸媒作用下所得之產物結果,其中包含一甲烷產率曲線2、一乙烷產率曲線3、一甲醇產率曲線4、及一二甲醚產量率線5,由生成產物之曲線分佈可知,藉由本發明自製之Cu-Zn-ZSM5觸媒係可有效自合成氣產出二甲醚及甲醇,而伴隨二甲醚產出之副產物則以甲烷與乙烷較多,並且隨溫度升高(>250℃)增多。故,經此足以驟證合成氣藉由本發明產製之觸媒係可直接產生二甲醚無誤。
請參閱『第5圖』所示,係本發明之溫度調變對選擇性關係示意圖。如圖所示:本發明自製觸媒時其溫度係具有可選擇性(Selectivity)地調變,其中並以合成二甲醚之理想溫度在250~280℃時具有>85%之選擇性,為可正確完成二甲醚之最佳選擇性範圍。
由上述可知,本發明自製之多功能觸媒,係同時兼具有甲醇合成與甲醇脫水兩種活性位置之觸媒,上述活性位置緊密接觸,不相互遮蔽,因而可提升觸媒活性。因此,在合成氣直接產製二甲醚反應中之脫水反應係在弱酸位置上進行,即弱酸位置數目越多,觸媒活性及產物選擇率也越高;另外,本發明自製之多功能觸媒亦具良好加乘效應,因酸性脫水組成之存在,可使甲醇合成活性組成趨於活潑,且易於還原,而甲醇合成活性組成之存在,則使酸性脫水組成之弱酸位置酸強度增加,進而可增強觸媒脫水能力,故使本發明具有可相對地提高整體反應之轉化率、二甲醚之反應選擇率及有效降低成本之優勢。若能進一步採用化學方法將觸媒表面添加少量改質成份,改變其活性中心性質,則對於提高觸媒性能,如低溫活性、選擇性及穩定性等,將有所助益。
綜上所述,本發明係一種合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,可有效改善習用之種種缺點,採用溶膠凝膠法,透過改變組成、凝膠沉澱及後處理條件,俾利提供調變觸媒之晶粒大小、晶型、表面結構及活性中心分布等性質,從而改善觸媒之性能,以製得兼具甲醇合成及甲醇脫水兩種活性位置之微粒徑之奈米觸媒者,進而使本發明之產生能更進步、更實用、更符合使用者之所須,確已符合發明專利申請之要件,爰依法提出專利申請。
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍;故,凡依本發明申請專利範圍及發明說明書內容所作之簡單的等效變化與修飾,皆應仍屬本發明專利涵蓋之範圍內。
11...步驟(A)提供合成觸媒
12...步驟(B)提供脫水觸媒
13...步驟(C)攪拌生成微粒
14...步驟(D)真空揮發
15...步驟(E)高溫煅燒
16...步驟(F)冷卻
17...步驟(G)氫氣煅燒還原
18...步驟(H)物理加工
2...甲烷產量曲線
3...乙烷產量曲線
4...甲醇產量曲線
5...二甲醚產量曲線
第1圖,係本發明之製備流程示意圖。
第2圖,係本發明Cu-Zn-Al觸媒之X光繞射(XRD)圖譜示意圖。
第3圖,係本發明以合成觸媒對合成氣應用之產物分佈示意圖。
第4圖,係本發明之溫度對產量關係示意圖。
第5圖,係本發明之溫度調變對選擇性關係示意圖。
第6圖,係習知之二甲醚工業生產方式示意圖。
11...步驟(A)提供合成觸媒
12...步驟(B)提供脫水觸媒
13...步驟(C)攪拌生成微粒
14...步驟(D)真空揮發
15...步驟(E)高溫煅燒
16...步驟(F)冷卻
17...步驟(G)氫氣煅燒還原
18...步驟(H)物理加工
Claims (7)
- 一種合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,係採用溶膠凝膠法選用適當之溶劑與界面活性劑形成與混合鹽溶液不互溶之有機相,運用成膠後表面張力之變化,使製備過程中生成之膠團粒子迅速轉移至該有機相中,藉以對膠團起隔離作用,透過阻止其再老化與乾燥過程中變大,進而製成微粒徑之奈米觸媒,其至少包含下列步驟:(A)提供合成觸媒步驟:提供一含有催化活性成分鹽類之乙醇溶液,其中,該催化活性成分係指提供含有一氧化碳(CO)加氫(H2 )活性中心之銅(Cu)、鋅(Zn)及鋁(Al)、或銅及鋅所組成之活性成分者;(B)提供脫水觸媒步驟:提供一含有脫水活性之微孔性固體載體;(C)攪拌生成微粒步驟:將上述含有催化活性成分鹽類之乙醇溶液,與上述固體載體於一溫度介於-5~4℃之間進行充分攪拌,並緩慢逐滴加入一含草酸之乙醇溶液使之混合沉澱,生成與該固體載體緊密結合之草酸鹽微粒;(D)真空揮發步驟:將上述緊密結合有草酸鹽微粒之固體載體置於一真空濃縮環境下,以真空揮發方式去除其中乙醇成分;(E)高溫煅燒步驟:將上述已去除乙醇成分之固體載體置於高溫爐中,在一溫度介於500±10℃之間進行高溫煅燒,以高溫煅燒方式將其中草酸有機物析出去除;(F)冷卻步驟:將經煅燒後之固體載體予以冷卻;(G)氫氣煅燒還原步驟:將上述冷卻後之固體載體置 於通入有氫氣氣氛之高溫爐中,在一溫度介於400±10℃之間進行高溫煅燒,脫附結合於該固體載體中之氧原子,並還原結合於該固體載體中之金屬觸媒微粒;(H)物理加工步驟:將上述經過一連串化學加工處理後之固體載體,經壓片、破碎及過篩之物理加工處理,即得一兼具甲醇合成及甲醇脫水兩種活性位置之Cu-Zn-Al觸媒;以及藉以上述各步驟,透過改變組成、凝膠沉澱及後處理條件,俾利提供調變觸媒之晶粒大小、晶型、表面結構及活性中心分布之性質,從而改善觸媒之性能者。
- 依據申請專利範圍第1項所述之合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,其中,該步驟(B)係提供含有脫水活性中心之分子篩、三氧化鋁(γ-Al2 O3 )或矽鋁化物之固體載體。
- 依據申請專利範圍第2項所述之合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,其中,該分子篩係為沸石(ZSM-5)。
- 依據申請專利範圍第1項所述之合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,其中,該步驟(C)係在0℃之溫度與大於300rpm轉速下進行充分攪拌。
- 依據申請專利範圍第1項所述之合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,其中,該金屬觸媒微粒係銅觸媒微粒。
- 依據申請專利範圍第1項所述之合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,其中,該金屬觸媒微粒係鋅觸媒微粒。
- 依據申請專利範圍第1項所述之合成甲醇及二甲醚之Cu-Zn-Al觸媒製備方法,其中,該金屬觸媒微粒係鋁觸媒微粒。
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