CN111511468B - 用于通过氧化酯化产生甲基丙烯酸甲酯的非均相催化剂 - Google Patents
用于通过氧化酯化产生甲基丙烯酸甲酯的非均相催化剂 Download PDFInfo
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- CN111511468B CN111511468B CN201880083173.0A CN201880083173A CN111511468B CN 111511468 B CN111511468 B CN 111511468B CN 201880083173 A CN201880083173 A CN 201880083173A CN 111511468 B CN111511468 B CN 111511468B
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 9
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- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000006709 oxidative esterification reaction Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 38
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010931 gold Substances 0.000 claims abstract description 18
- 229910052751 metal Chemical group 0.000 claims abstract description 14
- 239000002184 metal Chemical group 0.000 claims abstract description 14
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- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052737 gold Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 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
- 239000012071 phase Substances 0.000 claims description 2
- 229910001922 gold oxide Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 5
- 210000003278 egg shell Anatomy 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- UCGZDNYYMDPSRK-UHFFFAOYSA-L trisodium;gold;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[Na+].[Au].OS([S-])(=O)=O.OS([S-])(=O)=O UCGZDNYYMDPSRK-UHFFFAOYSA-L 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
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- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- 102000002322 Egg Proteins Human genes 0.000 description 3
- 108010000912 Egg Proteins Proteins 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- GDKAXSGMPFSRJY-UHFFFAOYSA-J 2-ethylhexanoate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O GDKAXSGMPFSRJY-UHFFFAOYSA-J 0.000 description 1
- 239000004251 Ammonium lactate Substances 0.000 description 1
- 244000132069 Carica monoica Species 0.000 description 1
- 235000014649 Carica monoica Nutrition 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000219823 Medicago Species 0.000 description 1
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-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
- 239000005388 borosilicate glass Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-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
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 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
- NVQGUGFHTHIDRH-UHFFFAOYSA-N oxotitanium(2+) pentane-2,4-dione Chemical compound O=[Ti++].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NVQGUGFHTHIDRH-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 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
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 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 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007858 starting material Substances 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
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
一种非均相催化剂，其包含载体和贵金属，其中所述载体包含硅，并且其中以硅原子和金属原子的总摩尔数计，所述催化剂包含0.1mol％到40mol％钛和0.1mol％到10mol％至少一种贵金属。所述贵金属可以为例如金/二氧化硅。
Description
背景技术
本发明涉及非均相催化剂。催化剂尤其可用于由异丁烯醛和甲醇制备甲基丙烯酸甲酯的方法中。
具有负载于二氧化硅上的贵金属与氧化铝和其它元素的组合的非均相催化剂为已知的，参见例如美国专利第US8461737B2号。然而，需要额外的具有改善的性质的催化剂颗粒。
发明内容
本发明涉及包含载体和贵金属的非均相催化剂，其中所述载体包含硅，并且其中所述催化剂包含0.1mol％到40mol％钛和0.1mol％到10mol％至少一种贵金属，其中摩尔百分比是以硅原子和金属原子的总摩尔数计。
本发明进一步涉及制备包含载体和贵金属的非均相催化剂的方法，其中所述载体包含硅和钛，并且其中所述催化剂包含0.1mol％到40mol％钛和0.1mol％到10mol％至少一种贵金属，其中摩尔百分比是以硅原子和金属原子的总摩尔数计；所述方法包含使包含硅的载体与钛盐和贵金属盐接触。
本发明进一步涉及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为重量百分比(wt％)，并且所有温度都以℃为单位。“贵金属”为金、铂、铱、锇、银、钯、铑和钌中的任一种。超过一种贵金属可以存在于催化剂中，在这种情况下，限值应用于所有贵金属总体。“金属”为周期表第1到12族中的元素，不包括氢，加上铝、镓、铟、铊、锡、铅和铋。“催化剂中心”为催化剂颗粒的质心，即在所有坐标方向上所有点的平均位置。直径为穿过催化剂中心的任何线性尺寸，并且平均直径为所有可能性直径的算术平均值。纵横比为最长直径与最短直径的比。
优选地，载体为包含耐火氧化物的颗粒；优选地，二氧化硅、二氧化钛、氧化镁或其组合；优选地，载体为二氧化硅或被其它耐火氧化物改性的二氧化硅。优选地，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。优选地，以硅原子和金属原子(即不包括氧和除硅以外的其它非金属元素)的总摩尔数计，载体包含有包含0.1mol％到40mol％、优选地至少0.1mol％、优选地至少1mol％、优选地不超过40mol％、优选地不超过30mol％钛的二氧化硅颗粒。优选地，以硅原子和金属原子的总摩尔数计，载体包含不超过10mol％、优选地不超过5mol％、优选地不超过2mol％、优选地不超过1mol％、优选地不超过0.5mol％铝。
优选地，催化剂颗粒的纵横比不超过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。颗粒的优选形状包括球形、圆柱形、矩形固体、环形、多叶形(例如苜蓿叶横截面(cloverleaf cross section))、具有多个孔的形状以及“马车车轮形”，优选地球形。也可以使用不规则形状。
优选地，以硅原子和金属原子的总摩尔数计，催化剂包含0.1mol％到10mol％至少一种贵金属、50mol％到95mol％Si、0.1mol％到40mol％Ti和0.1mol％到40mol％碱金属或碱土金属或其组合。优选地，催化剂包含至少55mol％、优选地至少60mol％、优选地至少65mol％、优选地至少70mol％、优选地不超过97mol％Si。优选地，催化剂包含至少0.1mol％、优选地至少1mol％、优选地至少5mol％、优选地不超过30mol％、优选地不超过20mol％、优选地不超过15mol％Ti。优选地，催化剂包含至少0.1mol％、优选地至少0.2mol％、优选地至少0.3mol％、优选地不超过7mol％、优选地不超过5mol％、优选地不超过3mol％贵金属。优选地，催化剂包含至少0.1mol％、优选地至少1mol％、优选地至少2mol％、优选地不超过30mol％、优选地不超过20mol％、优选地不超过15mol％碱金属或碱土金属。在本发明的一个优选实施例中，以硅原子和金属原子的总摩尔数计，催化剂包含不超过20mol％、优选地不超过10mol％、优选地不超过5mol％、优选地不超过2mol％、优选地不超过1mol％镁。在本发明的一个优选实施例中，以硅原子和金属原子的总摩尔数计，催化剂包含不超过20mol％、优选地不超过10mol％、优选地不超过5mol％、优选地不超过2mol％、优选地不超过1mol％碱土金属。
优选地，至少90wt％贵金属处于催化剂体积(即平均催化剂颗粒的体积)的外部80％、优选地外部60％、优选地外部50％、优选地外部40％、优选地外部30％、优选地外部25％中。优选地，针对具有沿着垂直于外表面的线测量的从其内表面到其外表面(颗粒的表面)的恒定距离的体积计算任何颗粒形状的外部体积。举例来说，对于球面颗粒，体积的外部x％为球面壳体，所述球面壳体的外表面为颗粒的表面并且其体积为整个球体体积的x％。优选地，至少95wt％、优选地至少97wt％、优选地至少99wt％贵金属处于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％)贵金属处于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的。
优选地，贵金属为金或钯，优选地金。
优选地，催化剂颗粒的平均直径为至少60微米、优选地至少100微米、优选地至少200微米、优选地至少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3毫米。载体的平均直径和最终催化剂颗粒的平均直径没有显著差异。
优选地，呈贵金属和载体百分比形式的贵金属的量为0.2wt％到5wt％、优选地至少0.5wt％、优选地至少0.8wt％、优选地至少1wt％、优选地至少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产生甲基丙烯酸甲酯(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)中用甲醇处理异丁烯醛。催化剂床包含催化剂颗粒并且位于可以发生流过催化剂床的流体流动的OER内。催化剂床中的催化剂颗粒通常通过固体壁和通过筛网保持在适当位置。在一些配置中，筛网处于催化剂床的相对端上并且固体壁处于侧面上，但在一些配置中，催化剂床可以被筛网完全包围。催化剂床的优选形状包括圆柱形、矩形固体和圆柱形壳体；优选地圆柱形。OER进一步包含有包含异丁烯醛、甲醇和MMA的液相以及包含氧气的气相。液相可以进一步包含例如异丁烯醛二甲基缩醛(MDA)和异丁酸甲酯(MIB)的副产物。优选地，液相处于40℃到120℃、优选地至少50℃、优选地至少60℃、优选地不超过110℃、优选地不超过100℃的温度下。优选地，催化剂床处于0psig到2000psig(101.3kPa到13890.8kPa)、优选地不超过2000kPa、优选地不超过1500kPa的压力下。优选地，催化剂床中的pH为4到10；优选地至少4.5、优选地至少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，催化剂床处于管式连续反应器中。
优选地，通过在存在载体的情况下在载体颗粒(优选地二氧化硅)上从钛盐中沉淀钛并且随后从金属盐水溶液中沉淀贵金属来产生催化剂。优选的钛盐包括乙酸钛、硫酸钛、含氧硫酸钛(IV)、氯化钛、氯氧化钛、双(乳酸铵)二氢氧化钛(IV)溶液、2-乙基己醇钛(IV)、丁醇钛(IV)、异丙醇钛(IV)和氧基乙酰基丙酮酸钛(IV)。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、氯化钯和乙酸钯。在一个优选实施例中，通过初步润湿技术产生被钛改性的载体，在所述初步润湿技术中将钛前体盐水溶液添加到多孔无机氧化物中以使得孔隙填充有溶液，并且随后通过干燥除去水。优选地，随后通过煅烧、还原或所属领域的技术人员已知的其它处理将钛盐分解到金属或金属氧化物中来处理所得材料。优选地，通过初步润湿、接着干燥并且优选地通过煅烧将贵金属添加到经煅烧的被钛改性的载体中。
煅烧优选地在250℃到600℃、优选地至少300℃、优选地不超过550℃的温度下进行。优选地，以逐步或连续的方式将温度升高到最终煅烧温度。
在另一个优选实施例中，通过沉积沉淀产生催化剂，在所述沉积沉淀中将多孔无机氧化物浸入含有合适的贵金属前体盐的水溶液中，并且随后通过调节溶液的pH使所述盐与无机氧化物的表面相互作用。随后，回收(例如通过过滤)所得处理过的固体，并且接着通过煅烧、还原或所属领域的技术人员已知的其它处理将贵金属盐分解到金属或金属氧化物中来将所述所得处理过的固体转化成成品催化剂。
实例
1号实例
单程固定床气泡塔反应器操作：
将由20wt％异丁烯醛、200ppm抑制剂和余量甲醇组成的饲料以40克/小时的速率进料到含有短前段硼硅玻璃珠、接着为5克催化剂的3/8"(9.5毫米)不锈钢管式反应器中。利用1号催化剂。还将含有含8％氧气的氮气的气体以足以在排气口中获得4.5％O2的速率进料到反应器中。在60℃和160psig(1200kPa)下操作反应器。将反应器的产物传送到液体-蒸汽分离器中并将蒸汽传送到冷凝器中，并且液体返回，不可冷凝气体去向排气口。结果描述于下表中。
1号催化剂制备：
通过初步润湿技术使用20g富士硅化学株式会社(Fuji Silysia Chemical,Ltd.)CARiACT Q-10载体作为起始材料并将钛添加到载体材料中来制备1号催化剂。具体地说，将10.5g异丙醇钛以及3g冰乙酸添加到于旋转设备中的催化剂中以确保溶液向载体材料的均匀分布。当添加时，溶液处于40℃下。随后，将改性的载体材料在略微真空下在60℃下干燥4小时，并且随后在空气中在环境压力下通过以下进行煅烧：将温度以5℃/分钟从环境温度缓慢升温到125℃，保持1小时，并且随后以5℃/分钟缓慢升温到250℃并保持1小时，随后以5℃/分钟缓慢升温到350℃并保持1小时，并且最后以5℃/分钟缓慢升温到450℃并保持4小时。接着，在40℃下通过初步润湿技术利用含0.83g金硫代硫酸钠的10g去离子水将金添加到载体中。在空气中使用与上文相同的加热概况干燥并煅烧所得催化剂。用配备有能量色散光谱(EDS)的扫描电子显微镜(SEM)进行的催化剂分析清楚地指示，Ti和Au两者的蛋壳沉积存在，其中Au优选地仅位于Ti沉积之处。发现Ti和Au蛋壳厚度为约50微米或更小。在1mm直径催化剂的外部50微米中估计负载量为10mol％的情况下，估计钛的局部负载量与Ti/(Ti+Si)一样至多40mol％。
2号实例(比较)
间歇式再循环固定床气泡塔反应器操作：
制备包含10wt％异丁烯醛、200ppm抑制剂和余量甲醇的150g饲料溶液，并放置在充当气体分离容器的300ml
反应器中。将容器液体维持在约20℃的温度下。将液体饲料以7毫升/分钟从气体分离容器泵送到竖直定向的固定床反应器的底部中。将空气和氮气混合以获得7.8mol％氧气，并与液体饲料混合，之后进入固定床反应器。固定床反应器为使用外部加热器维持在60℃下的加套1/4"(6.4mm)不锈钢管。反应器自身装有2mm玻璃珠以填充约18英寸(46厘米)管，随后装有催化剂。反应器顶部处的剩余空隙填充有3mm玻璃珠。将离开反应器顶部的液体和气体传送到冷凝器中，并不可冷凝气体被排出，而液体再循环回到气体分离容器中。2号催化剂以及下文3号、4号和5号实例的催化剂都以此方式运行。
2号催化剂制备：
通过初步润湿溶解于100g水中以制造水溶液的4.1g硫代硫酸钠金并且随后放置在100g富士硅化学株式会社CARiACT Q-20二氧化硅载体材料上来制备2号催化剂。将样品在120℃下干燥1小时，接着在400℃下煅烧4小时。
3号实例
3号催化剂制备：
通过以下步骤制备3号催化剂。首先，将由51.7g异丙醇钛和28.5g冰乙酸组成的钛前体储备溶液混合并在环境温度下搅拌。随后，通过将27.9g上述钛储备溶液浸渍到20g富士硅化学株式会社CARiACT Q-10二氧化硅载体材料的初步润湿点来制备载体材料。随后，将样品在125℃下干燥1小时，接着在250℃下煅烧1小时，在350℃下煅烧1小时，并在450℃下煅烧隔夜，其中在不同温度设定之间缓慢升温速率为5℃/分钟。通过将含有0.4g硫代硫酸钠金和16g去离子水的溶液浸渍到10g上述载体材料中，达到其初步润湿点来实现金沉积。随后，将样品在120℃下干燥1小时，接着在400℃下煅烧4小时。用配备有能量色散光谱(EDS)的扫描电子显微镜(SEM)进行的催化剂分析清楚地指示，Ti和Au两者的蛋壳沉积存在，其中Au优选地仅位于Ti沉积之处。发现Ti和Au蛋壳厚度为约300微米或更小。
4号实例
4号催化剂制备：
通过以下步骤制备4号催化剂。首先，通过将异丙醇钛浸渍到10g富士硅化学株式会社CARiACT Q-10二氧化硅载体材料的初步润湿点来制备载体材料。随后，将样品在125℃下干燥1小时，接着在250℃下煅烧1小时，在350℃下煅烧1小时，在450℃下煅烧1小时并在550℃下煅烧12小时，其中在不同温度设定之间缓慢升温速率为5℃/分钟。通过将含有0.25g硫代硫酸钠金和9g去离子水的溶液浸渍到6g上述载体材料的初步润湿点来实现金沉积。随后，将样品在120℃下干燥1小时，接着在400℃下煅烧4小时。
5号实例
5号催化剂制备：
通过以下步骤制备5号催化剂。首先，通过将硝酸镁六水合物浸渍到10g富士硅化学株式会社CARiACT Q-10二氧化硅载体材料的初步润湿点来制备载体材料。随后，将样品在120℃下干燥1小时，接着在450℃下煅烧4小时，其中在不同温度设定之间缓慢升温速率为5℃/分钟。混合8.5g量的异丙醇钛和1.5g量的乙酸，得到钛前体溶液，并且随后将3.1g钛前体溶液浸渍到上述经煅烧的Mg-SiO2中。随后，将样品在120℃下干燥1小时，接着在550℃下煅烧6小时，其中在不同温度设定之间缓慢升温速率为5℃/分钟。通过将含有0.3g硫代硫酸钠金和8g去离子水的溶液浸渍到8g上述载体材料的初步润湿点来实现金沉积。随后，将样品在120℃下干燥1小时，接着在400℃下煅烧4小时。所得样品含有总计4.7wt％Mg和4wt％Ti/Si和1.5wt％负载于所述材料上的Au。不评估样品来确定是否存在蛋壳沉积。
催化剂性能：
*标准化MMA选择率为以异丁烯醛反应物形式起源之产物当中的MMA％。以100％MMA产物计，MIB以ppm(重量)为单位来报告。
抗压强度：
通过将颗粒压碎到机械故障点来直接测量催化剂或催化剂载体颗粒的机械强度。使用Mecmesin M100EC进行抗压强度测试。将单个颗粒放置在平台上并使顶部柱塞按压颗粒直到负荷达到峰值并且材料失效为止。使用Shimpo FGE-100X计量器记录峰值负荷。对25个单独颗粒进行重复测试以获得任何给定材料的抗压强度的统计平均值。结果列表于下方。
Claims (10)
1.一种非均相催化剂，其包含载体和贵金属，其中所述载体包含硅，并且其中所述催化剂包含0.1mol％到40mol％钛和0.1mol％到10mol％至少一种贵金属，其中摩尔百分比是以硅原子和金属原子的总摩尔数计，呈贵金属和载体百分比形式的贵金属的量为0.2wt％到2.5wt％。
2.根据权利要求1所述的催化剂，其中所述贵金属选自由金、钯和其组合组成的组。
3.根据权利要求2所述的催化剂，其中所述催化剂的平均直径为60微米到10毫米。
4.根据权利要求3所述的催化剂，其中所述催化剂包含0.1mol％到8mol％至少一种贵金属、60mol％到95mol％硅、0.1mol％到20mol％钛和0.1mol％到20mol％碱金属或碱土金属。
5.根据权利要求4所述的催化剂，其中所述载体为二氧化硅。
6.根据权利要求5所述的催化剂，其中所述贵金属为金。
7.一种催化剂床，其包含(i)包含载体和贵金属的非均相催化剂，其中所述载体包含硅和钛，并且其中所述催化剂包含0.1mol％到40mol％钛、0.1mol％到10mol％至少一种贵金属，其中摩尔百分比是以硅原子和金属原子的总摩尔数计；和(ii)包含异丁烯醛、甲醇和甲基丙烯酸甲酯的液相，呈贵金属和载体百分比形式的贵金属的量为0.2wt％到2.5wt％。
8.根据权利要求7所述的催化剂床，其中所述贵金属选自由金、钯和其组合组成的组。
9.根据权利要求8所述的催化剂床，其中所述催化剂的平均直径为200微米到10毫米，并且所述催化剂床包含有包含氧气的气相。
10.根据权利要求9所述的催化剂床，其中所述催化剂包含0.1mol％到8mol％至少一种贵金属、60mol％到95mol％硅、0.1mol％到20mol％钛和0.1mol％到20mol％碱金属或碱土金属。
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| PCT/US2018/065372 WO2019139719A1 (en) | 2018-01-10 | 2018-12-13 | Heterogeneous catalyst for the production of methyl methacrylate by oxidative esterification |
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| CN112165987B (zh) * | 2018-06-28 | 2024-05-17 | 陶氏环球技术有限责任公司 | 非均相催化剂 |
| JP2023519126A (ja) * | 2020-03-17 | 2023-05-10 | ダウ グローバル テクノロジーズ エルエルシー | 長寿命触媒による酸化的エステル化の方法及び触媒 |
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| CN111511468A (zh) | 2020-08-07 |
| MX2020006629A (es) | 2020-09-22 |
| US11577225B2 (en) | 2023-02-14 |
| SG11202005796UA (en) | 2020-07-29 |
| KR20200105854A (ko) | 2020-09-09 |
| WO2019139719A1 (en) | 2019-07-18 |
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