CN111050909B - 非均相催化剂 - Google Patents
非均相催化剂 Download PDFInfo
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- CN111050909B CN111050909B CN201880056491.8A CN201880056491A CN111050909B CN 111050909 B CN111050909 B CN 111050909B CN 201880056491 A CN201880056491 A CN 201880056491A CN 111050909 B CN111050909 B CN 111050909B
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- -1 vanadia Chemical compound 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 14
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 10
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- 102000002322 Egg Proteins Human genes 0.000 description 3
- 108010000912 Egg Proteins Proteins 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 210000003278 egg shell Anatomy 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OBSHSWKHUYGFMF-UHFFFAOYSA-N 3,3-dimethoxy-2-methylprop-1-ene Chemical compound COC(OC)C(C)=C OBSHSWKHUYGFMF-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 2
- AGHLUVOCTHWMJV-UHFFFAOYSA-J sodium;gold(3+);2-sulfanylbutanedioate Chemical compound [Na+].[Au+3].[O-]C(=O)CC(S)C([O-])=O.[O-]C(=O)CC(S)C([O-])=O AGHLUVOCTHWMJV-UHFFFAOYSA-J 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015045 gold sodium thiomalate Drugs 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000006709 oxidative esterification reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004576 sand 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- TWZQFPNFWDJPRN-UHFFFAOYSA-J sodium dioxido-oxo-sulfanylidene-lambda6-sulfane gold(3+) hydrate Chemical compound O.S(=S)(=O)([O-])[O-].[Na+].[Au+3].S(=S)(=O)([O-])[O-] TWZQFPNFWDJPRN-UHFFFAOYSA-J 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 150000007944 thiolates Chemical group 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种包含载体和贵金属的非均相催化剂。所述催化剂的平均直径是至少200微米,并且至少90wt%的所述贵金属是在催化剂体积的外部50%中。
Description
背景技术
本发明涉及一种非均相催化剂。所述催化剂尤其适用于由甲基丙烯醛和甲醇制备甲基丙烯酸甲酯的方法中。
已知具有贵金属集中在催化剂的外部区域中的非均相催化剂,参见例如美国专利第6,228,800号。然而,需要贵金属在表面附近的浓度较高的较大催化剂粒子。
发明内容
本发明涉及一种包含载体和贵金属的非均相催化剂,其中所述催化剂的平均直径是至少200微米并且至少90wt%的所述贵金属是在催化剂体积的外部50%中。
本发明还涉及一种包含所述催化剂的催化剂床。
具体实施方式
除非另外指示,否则所有百分比组成都是以重量百分比(wt%)计,并且所有温度都是以℃为单位。贵金属是金、铂、铱、锇、银、钯、铑以及钌中的任一种。催化剂中可存在超过一种贵金属,在这种情况下,要对所有贵金属的总量加以限制。“催化剂中心”是催化剂粒子的质心,即在所有坐标方向上所有点的平均位置。直径是穿过催化剂中心的任何线性尺寸,并且平均直径是所有可能直径的算术平均值。纵横比是最长与最短直径的比率。
优选地,载体是耐火氧化物粒子;优选地是γ-氧化铝、δ-氧化铝或θ-氧化铝、二氧化硅、氧化镁、二氧化钛、氧化锆、氧化铪、氧化钒、氧化铌、氧化钽、二氧化铈、氧化钇、氧化镧或其组合;优选地是γ-氧化铝、δ-氧化铝或θ-氧化铝。优选地,在催化剂的包含贵金属的部分中,载体的表面积大于10m2/g,优选地大于30m2/g,优选地大于50m2/g,优选地大于100m2/g,优选地大于120m2/g。在催化剂的包含极少或不包含贵金属的部分中,载体的表面积可以小于50m2/g,优选地小于20m2/g。
优选地,催化剂粒子的纵横比不超过10:1,优选地不超过5:1,优选地不超过3:1,优选地不超过2:1,优选地不超过1.5:1,优选地不超过1.1:1。所述粒子的优选形状包括球形、圆柱形、矩形固体、环形、多叶形(例如苜蓿叶形横截面)、具有多个孔的形状以及“马车车轮形”;优选地为球形。也可以使用不规则形状。
优选地,至少90wt%的所述贵金属是在催化剂体积(即,平均催化剂粒子的体积)的外部40%中,优选地在外部35%中,优选地在外部30%中,优选地在外部25%中。优选地,任何粒子形状的外部体积都是针对沿着垂直于外表面的线测量的从其内表面至其外表面(粒子的表面)具有恒定距离的体积计算。例如,对于球形粒子,体积的外部x%是球形壳体,所述球形壳体的外表面是粒子的表面,并且其体积是整个球体体积的x%。优选地,至少95wt%、优选地至少97wt%、优选地至少99wt%的贵金属是在催化剂的外部体积中。优选地,至少90wt%(优选地至少95wt%、优选地至少97wt%、优选地至少99wt%)的贵金属在距表面不超过催化剂直径的15%、优选地不超过10%、优选地不超过8%、优选地不超过6%的距离内。距表面的距离是沿着垂直于表面的线测量。
优选地,贵金属是金或钯,优选地是金。
优选地,催化剂粒子的平均直径是至少300微米,优选地至少400微米,优选地至少500微米,优选地至少600微米,优选地至少700微米,优选地至少800微米;优选地不超过30毫米,优选地不超过20毫米,优选地不超过10毫米,优选地不超过5毫米,优选地不超过4毫米。载体的平均直径与最终催化剂粒子的平均直径无明显不同。
优选地,以贵金属和载体的百分比计的贵金属的量是0.2至5wt%,优选地是至少0.5wt%,优选地是至少0.8wt%,优选地是至少1wt%,优选地是至少1.2wt%;优选地不超过4wt%,优选地不超过3wt%,优选地不超过2.5wt%。
本发明的催化剂可用于生产甲基丙烯酸甲酯(MMA)的方法中,所述方法包含在含有催化剂床的氧化酯化反应器(OER)中用甲醇处理甲基丙烯醛。催化剂床包含催化剂粒子并且定位于使液流可以穿过催化剂床的OER内。催化剂床中的催化剂粒子典型地通过固体壁和通过筛网保持在适当的位置。在一些配置中,所述筛网是在催化剂床的相对端上并且固体壁是在侧面上,不过,在一些配置中,催化剂床可被筛网完全包围。催化剂床的优选形状包括圆柱形、矩形实心和圆柱形壳;优选地是圆柱形。OER还包括含甲基丙烯醛、甲醇和MMA的液相以及含氧气的气相。液相还可包含副产物,例如甲基丙烯醛二甲基乙缩醛(MDA)和异丁酸甲酯(MIB)。优选地,液相的温度是40至120℃;优选地是至少50℃,优选地是至少60℃;优选地不超过110℃,优选地不超过100℃。优选地,催化剂床的压力是0至2000psig(101kPa至14MPa);优选地不超过2000kPa,优选地不超过1500kPa。优选地,催化剂床中的pH值是4至10;优选地是至少4.5,优选地是至少5;优选地不超过9,优选地不超过8,优选地不超过7.5,优选地不超过7,优选地不超过6.5。优选地,催化剂床是在管状连续反应器或连续搅拌槽反应器中。
优选地,催化剂是通过在载体存在下,从金属盐的水溶液沉淀贵金属制造的。优选的贵金属盐包括四氯金酸、金硫代硫酸钠、金硫代苹果酸钠、氢氧化金、硝酸钯、氯化钯以及乙酸钯。在一个优选实施例中,催化剂是通过初湿技术制造,其中将适合贵金属前驱体盐的水溶液添加至多孔无机氧化物中,使得孔被该溶液填充,接着通过干燥去除水。接着,通过煅烧、还原或本领域的技术人员已知的其它处理将贵金属盐分解为金属或金属氧化物,由此将所得材料转化成最终的催化剂。优选地,在所述溶液中存在包含至少一个羟基或羧酸取代基的C2-C18硫醇。优选地,包含至少一个羟基或羧酸取代基之C2-C18硫醇具有2至12个,优选地具有2至8个,优选地具有3至6个碳原子。优选地,硫醇化合物包含不超过4个、优选地不超过3个、优选地不超过2个总羟基和羧酸基团。优选地,硫醇化合物具有不超过2个,优选地不超过1个硫醇基。如果硫醇化合物包含羧酸取代基,则其可以呈酸形式、共轭碱形式或其混合物存在。硫醇组分也可以呈其硫醇(酸)形式或其共轭碱(硫醇盐)形式存在。尤其优选的硫醇化合物包括硫代苹果酸、3-巯基丙酸、硫代乙醇酸、2-巯基乙醇以及1-硫代甘油,包括其共轭碱。
在另一个优选实施例中,催化剂是通过沉积沉淀法制造,其中将多孔无机氧化物浸入含有适合贵金属前驱体盐的水溶液中,接着通过调整该溶液的pH值使该盐与无机氧化物的表面相互作用。接着,回收(例如通过过滤)由此得到的处理过的固体,接着通过煅烧、还原或本领域的技术人员已知的其它处理将贵金属盐分解为金属或金属氧化物,由此转化为最终的催化剂。
实例
催化剂778:“蛋壳式”金催化剂
在搅拌下,将0.3088g金硫代苹果酸钠溶解于8.908g去离子水中。接下来,将10.0243g预先储存于120℃的干燥炉中的氧化铝(3.2mm球体,Norpro SA6275,批号2016910048)放入陶瓷坩埚中。在周期性搅拌下,使用刮勺逐滴添加金盐水溶液,直至载体达到初湿点。
在120℃下干燥所得材料1小时,接着在马弗炉(muffle furnace)中,在300℃(5℃/min匀变速率)下煅烧4小时。接着,将由此得到的紫色催化剂球储存于琥珀色小瓶中待用。通过NAA进行的元素分析披露以下元素组成:
描述 | Au,wt% | Na,ppm | Cl,ppm |
催化剂778 | 1.38±0.05 | 1000±30 | 340±20 |
催化剂780:均匀金催化剂(比较)
将0.3918g金硫代硫酸钠水合物溶解于9.0567g去离子水中。将10.0368g预先储存于120℃的干燥炉中的氧化铝样品(3.2mm球体,Norpro SA6275,批号2016910048)放入陶瓷坩埚中。在周期性搅拌下,使用刮勺逐滴添加金盐水溶液,直至载体达到初湿点。
在120℃下干燥所得材料1小时,接着在马弗炉中,在300℃(5℃/min匀变速率)下煅烧4小时。接着,将由此得到的紫色催化剂球储存于琥珀色小瓶中待用。通过NAA进行的元素分析披露以下元素组成:
对催化剂进行EDS扫描,结果如下。
催化剂780(比较)
wt%Au | 距催化剂外缘的距离,以微米为单位 | 催化剂的体积% |
95 | 750 | 85% |
90 | 680 | 81% |
催化剂780的数据显示,90wt%的金是在外缘的680微米内,对应于催化剂体积的外部81%;并且95wt%是在750微米内,或对应于外部85%。
催化剂778
wt%Au | 距催化剂外缘的距离,以微米为单位 | 催化剂的体积% |
95 | 75 | 13.4% |
90 | 70 | 12.6% |
催化剂778(“蛋-壳式”)的数据显示,90wt%的金是在外缘的70微米内,对应于催化剂体积的外部12.6%;并且95wt%是在75微米内,或对应于外部13.4%。
催化剂测试
在以滴流模式操作的连续固定床反应器中评价催化剂。在每种情况下,将约0.5g催化剂与碳化硅粒度砂混合以确保均匀润湿。将催化剂床夹在各玻璃珠层之间。在60℃和160psig(1200kPa)下,利用6(用20sccm空气和50sccm He获得)或21mol%O2的进口氧气组成,以70sccm气体流动速率操作反应器。以0.07mL/min流动速率引入液体进料(含10wt%甲基丙烯醛的甲醇)。随时间变化的性能、以空时产率计的MMA速率以及MIB含量(以100%MMA计的ppm)显示于下表中。
数据显示,在高氧气水平下,形成的副产物MIB较少。然而,在低氧气水平下,如在朝向催化剂床中氧气耗尽的一端存在的氧气水平下,本发明的“蛋-壳式”催化剂提供明显降低的MIB水平。本发明催化剂的空时产率在两种氧气水平下都很优良,尤其是在低氧气水平下。
Claims (6)
1. 一种包含载体和贵金属的非均相催化剂,其中所述催化剂的平均直径是400微米至10毫米并且至少95 wt%的所述贵金属是在催化剂体积的外部15%中;其中所述催化剂是通过在载体存在下,从金属盐的水溶液沉淀贵金属制造的,在所述溶液中存在包含至少一个羟基或羧酸取代基的C2-C18硫醇;其中所述贵金属选自由金和钯组成的组。
2.根据权利要求1所述的催化剂,其中所述载体选自由以下组成的组:γ-氧化铝、δ-氧化铝或θ-氧化铝、二氧化硅、氧化镁、二氧化钛、氧化钒、二氧化铈、氧化镧及其组合。
3.根据权利要求2所述的催化剂,其中所述催化剂的纵横比不超过3:1。
4.一种催化剂床,其包含(i)非均相催化剂,其中所述催化剂包含载体和贵金属,并且其中所述催化剂的平均直径是400微米至10毫米并且至少95wt%的所述贵金属是在催化剂体积的外部15%中;以及(ii)包含甲基丙烯醛、甲醇和甲基丙烯酸甲酯的液相;其中所述催化剂是通过在载体存在下,从金属盐的水溶液沉淀贵金属制造的,在所述溶液中存在包含至少一个羟基或羧酸取代基的C2-C18硫醇。
5.根据权利要求4所述的催化剂床,其中所述催化剂床还包括含氧气的气相。
6.根据权利要求5所述的催化剂床,其中所述贵金属选自由金和钯组成的组。
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