CN116174043A - 一种负载型醋酸烯丙酯催化剂及其制备方法和应用 - Google Patents
一种负载型醋酸烯丙酯催化剂及其制备方法和应用 Download PDFInfo
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- CN116174043A CN116174043A CN202310000459.0A CN202310000459A CN116174043A CN 116174043 A CN116174043 A CN 116174043A CN 202310000459 A CN202310000459 A CN 202310000459A CN 116174043 A CN116174043 A CN 116174043A
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- Prior art keywords
- catalyst
- active component
- allyl acetate
- silicon carbide
- reaction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- -1 [ (2-pyridyl) phenyl ] sodium Chemical compound 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000017 hydrogel Substances 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229930012538 Paclitaxel Natural products 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 229960001592 paclitaxel Drugs 0.000 claims abstract description 5
- RCINICONZNJXQF-MZXODVADSA-N taxol Chemical compound O([C@@H]1[C@@]2(C[C@@H](C(C)=C(C2(C)C)[C@H](C([C@]2(C)[C@@H](O)C[C@H]3OC[C@]3([C@H]21)OC(C)=O)=O)OC(=O)C)OC(=O)[C@H](O)[C@@H](NC(=O)C=1C=CC=CC=1)C=1C=CC=CC=1)O)C(=O)C1=CC=CC=C1 RCINICONZNJXQF-MZXODVADSA-N 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 59
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 34
- 239000011148 porous material Substances 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 28
- 238000011068 loading method Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 235000011056 potassium acetate Nutrition 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000004873 anchoring Methods 0.000 abstract description 3
- 150000001340 alkali metals Chemical group 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 239000010949 copper Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011734 sodium Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000010668 complexation reaction Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000014528 Pholiota nameko Nutrition 0.000 description 2
- 244000168667 Pholiota nameko Species 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101150002998 LCAT gene Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract
本发明公开了一种负载型醋酸烯丙酯催化剂及其制备方法和应用,所述催化剂含有载体,以及载体上负载的活性组分、配体、助活性组分;所述载体为碳化硅材料;所述活性组分选自金属Pd、Au、Cu;所述助活性组分选自碱金属醋酸盐;所述配体选自异丙基丙烯酰胺、(4,4'‑二叔丁基‑2,2'‑联吡啶)双[(2‑吡啶基)苯基]钠、三联吡啶氯化钠、紫杉醇、热敏水凝胶。本发明制得一种整体呈“蜂窝状”结构,内部组分呈“外多内少”分布的负载型醋酸烯丙酯催化剂。本发明制备的催化剂具有组成均匀牢固锚定,导热性能好,稳定性好,催化剂寿命长等特点,且催化剂时空收率高,产品选择性高。
Description
技术领域
本发明涉及一种负载型醋酸烯丙酯催化剂及其制备方法,具体涉及一种用于醋酸、氧气和丙烯合成醋酸烯丙酯的催化剂。
背景技术
醋酸烯丙酯是一种微溶于水,易溶于醇和醚,能溶于丙酮的无色易燃液体,主要用于生产丙烯醇及环氧氯丙烷。
EP0361484A2公开了一种负载主活性组分钯和助活性组分铜催化剂的制备方法,通过将贵金属钯和助剂铜制备成混合液浸渍在载体上,然后经过碱性沉淀剂进行沉淀,还原气氛还原,再经洗涤,干燥,浸渍醋酸钾后干燥得到催化剂。该方法得到的催化剂的空时收率和选择性均较低。
TW161027B公开了一种负载主活性组分贵金属和助活性组分金属的催化剂的制备方法。该方法采用氧化铝、二氧化矽、活性碳、二氧化矽一氧化铝、浮石及氧化钛为载体,采用钯为活性组分,铅、铜、钌、铼为助剂,通过浸渍,还原得到催化剂。通过该方法制备的催化剂活性组分和助剂极易流失,活性和选择性差,难以达到工业化生产要求。
CN106582871B公开了一种制备醋酸烯丙酯的方法,其具体制备过程如下:(1)将改性金属元素的氢氧化物或氧化物与硅溶胶混合得到的涂覆液涂覆在多孔二氧化硅表面通过干燥被烧得到载体;(2)将所述载体浸渍含Pd化合物和含Cu化合物的浸渍液得到催化剂前体I;(3)用碱性溶液使含Pd化合物和含Cu化合物转化为沉淀型得到催化剂前体II;(4)将所述沉淀型中的化合态Pd和化合态Cu还原为金属Pd和金属Cu得到催化剂前体III;(5)浸渍助催化剂溶液,干燥得到所述催化剂。通过该方法得到的催化剂能在一定程度上解决催化剂活性和选择性低的问题,但活性组分分布状态差,难以维持长时间的活性和选择性,易造成活性组分的流失,不适用于工业化生产。
以上发明通过将活性组分和助剂直接浸渍在载体表面制备的醋酸烯丙酯催化剂,存在活性低,选择性差,活性组分易流失,稳定性不足,寿命短等问题,不适用于工业化生产等缺点。
因此,希望在已有的技术基础上,通过对催化剂及催化剂制备方法的改进,提出一种更具工业应用价值的醋酸烯丙酯的催化剂及制备方法。
发明内容
针对现有技术中存在的上述不足,本发明提供一种负载型醋酸烯丙酯催化剂及其制备方法。所述催化剂含有载体,以及载体上负载的活性组分及配体、助活性组分,催化剂整体呈“蜂窝状”结构,活性组分呈“外多内少”状态分布。
本发明通过将含活性组分的金属盐配制成溶液同配体进行配位后负载于载体上,经过沉淀和还原后,再将助剂金属盐配成溶液进行沉淀浸渍制得一种整体呈“蜂窝状”结构,内部组分呈“外多内少”分布的负载型醋酸烯丙酯催化剂。本发明制备的催化剂具有组成均匀牢固锚定,导热性能好,稳定性好,催化剂寿命长等特点,且催化剂时空收率高,产品选择性高。
为达上述目的,本发明采用的技术方案如下:
本发明提供一种负载型醋酸烯丙酯催化剂,所述催化剂含有载体,以及载体上负载的活性组分、配体、助活性组分;
所述载体为碳化硅材料;
所述活性组分选自金属Pd、Au、Cu中的至少一种;
所述助活性组分选自碱金属醋酸盐中的至少一种,优选为醋酸钠和/或醋酸钾;
所述配体选自异丙基丙烯酰胺、(4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]钠、三联吡啶氯化钠、紫杉醇、热敏水凝胶中的至少一种。
本发明中,所述载体为碳化硅材料,选自碳化硅球、碳化硅棒和碳化硅环中的至少一种,更优选为碳化硅球;
所述碳化硅材料,粒径为1~5mm,优选2~3mm。
本发明中,所述活性组分负载量为0.1~10.0wt%,优选1~10.0wt%,基于载体质量计。
本发明中,所述助活性组分负载量为1.0~10.0wt%,优选1.0~5.0wt%,基于载体质量计。
本发明中,所述配体负载量为0.05~20.0wt%,优选0.1~10.0wt%,基于载体质量计。
本发明中,所述醋酸烯丙酯催化剂,粒径为1~5mm,优选2~3mm;比表面积为50~800m2/g,优选200~600m2/g;孔容为0.2~1.0cm3/g,优选0.2~0.6cm3/g;孔径为5~20nm,优选10~15nm。
本发明中,所述醋酸烯丙酯催化剂,具有“蜂窝状”结构,内部组分呈“外多内少”分布,优选地,所述活性组分自壳层每向内延伸10μm,活性组分浓度降低10~20wt%。
在本发明的具体实施方式中,作为优选举例,本发明提供一种上述负载型醋酸烯丙酯催化剂的制备方法,步骤包括:
(1)将含活性组分的金属盐配制成溶液,然后加入载体和配体进行配位反应,再加入沉淀剂进行沉淀反应,得到含前驱体A的反应液;
(2)向步骤(1)的反应液中加入还原剂进行还原反应,再经洗涤、干燥,得到前驱体B;
(3)将步骤(2)的前驱体B加入到含助活性组分的溶液中浸渍,取出后干燥,得到负载型醋酸烯丙酯催化剂。
本发明步骤(1)中,所述含活性组分的金属盐溶液为水溶液,浓度为5~30wt%,优选10~20wt%;
所述含活性组分的金属盐选自Pd、Au、Cu的氯化盐、硝酸盐、醋酸盐中的至少一种,优选Pd、Au和Cu的氯化盐中的至少一种。
本发明步骤(1)中,所述载体选自碳化硅材料,优选碳化硅球、碳化硅棒和碳化硅环中的至少一种,更优选为碳化硅球;
所述碳化硅材料,粒径为1~5mm,优选2~3mm。
本发明步骤(1)中,所述含活性组分的金属盐溶液,以其中的金属盐计,与载体混合的质量比为1:1~100,优选1:2~50。
本发明步骤(1)中,所述配体选自异丙基丙烯酰胺、(4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]钠、三联吡啶氯化钠、紫杉醇、热敏水凝胶中的至少一种,优选为异丙基丙烯酰胺;
所述配体与载体的质量比为1:5~200,优选1:10~100。
本发明步骤(1)中,所述沉淀剂选自氢氧化钾、氢氧化钠、碳酸钾、碳酸钠、硅酸钾、硅酸钠中的至少一种,优选为氢氧化钠、硅酸钠、碳酸钠中的至少一种;
所述沉淀剂用量,为含活性组分的金属盐溶液中金属摩尔量的1~20倍,优选1~5倍;
优选地,所述沉淀剂配制为水溶液使用,浓度为1~20wt%,优选5~10wt%。
本发明步骤(1)中,所述配位反应,温度为10~50℃,优选20~30℃;时间为10~72h,优选20~40h。
本发明步骤(1)中,步骤(1)中,所述沉淀反应,温度为10~50℃,优选20~30℃;时间为10~72h,优选20~40h。
本发明步骤(2)中,所述还原剂选自乙烯、丙烯、氢气、水合肼、甲醛中的至少一种,优选为氢气、丙烯、水合肼中的至少一种;
所述还原剂的加入量,为步骤(1)中含活性组分的金属盐溶液中金属摩尔量的0.5~20倍,优选1~15倍。
本发明步骤(2)中,所述还原反应,温度为10~50℃,优选20~30℃;时间为5~40h,优选10~20h。
本发明步骤(2)中,所述干燥温度为100~150℃;干燥时间为2~10h。
本发明步骤(3)中,所述含助活性组分的溶液为水溶液,浓度为1~20wt%,优选5~10wt%;
所述助活性组分选自碱金属醋酸盐中的至少一种,优选为醋酸钾;
所述前驱体B与含助活性组分的溶液的质量比为1:0.1~20,优选1:0.2~10。
本发明步骤(3)中,所述浸渍,温度为10~50℃,时间为5~36h。
本发明步骤(3)中,所述干燥,温度为100~150℃,时间为2~10h。
本发明提供的醋酸烯丙酯催化剂具有特别设计的“蜂窝状”结构,能够使催化剂活性组分位置分布均匀,具有良好的分散性和导热性,并使得催化剂具有优异的活性和选择性。本发明通过载体与配体配位反应同时负载活性组分形成具有特定“蜂窝状”且具有良好导热性的催化剂结构,不但能够大大提高催化剂的导热性,“蜂窝状”结构还能够使得催化剂的活性组分分布在特定的位置上,分散度高,使得催化剂反应放热不会过于集中,避免因反应热难以移除造成的产品选择性低,催化剂稳定性和寿命差。同时,本发明催化剂活性组分具有“外多内少”的分布状态,能够使的原料在接触催化剂时及时进行转化,并迅速脱附,避免大量原料内部进行反应导致扩散困难以及发生过度反应造成活性和选择性低,并且形成过度裂化产品堵塞孔道,覆盖活性位点。本发明所选载体以及配体协同作用还能够在制备过程中锚定活性组分并与其形成更加稳固的结构,以保证在发挥催化作用的同时不会脱落造成损失,提高经济性。热敏性配体能够及时对反应过程中生成的离子态活性组分进行转化,使其还原为单质态活性组分,重新发挥催化作用。
本发明同时提供了上述醋酸烯丙酯催化剂的应用,适用于醋酸、氧气和丙烯合成醋酸烯丙酯。
作为优选,本发明提供一种醋酸烯丙酯的制备方法,步骤包括:采用固定床反应器,在上述催化剂的存在下,将丙烯、氧气、醋酸、水混合进行反应制备醋酸烯丙酯。
本发明中,所述丙烯与氧气、醋酸、水的摩尔比1:0.3~1:0.2~1:0.3~1,例如1:0.4:0.5:0.5;
本发明中,所述反应,温度为120~180℃,优选140~170℃;压力为0.6~0.9MPaG,优选0.65~0.85MPaG;反应体积空速为1500~2500h-1,优选1800~2000h-1。
与现有技术相比,本发明技术方案有益效果在于:
本发明醋酸烯丙酯催化剂具有特别设计的“蜂窝状”结构,能够大大提高催化剂的导热性,且活性组分分散度高,使得催化剂反应放热不会过于集中,避免因反应热难以移除造成的产品选择性低,催化剂稳定性和寿命差。
活性组分“外多内少”的分布状态能够使的原料在接触催化剂时及时进行转化,并迅速脱附,避免大量原料内部进行反应导致扩散困难以及发生过度反应造成活性和选择性低,并且形成过度裂化产品堵塞孔道,覆盖活性位点。
本发明所选载体以及配体能够在制备过程中锚定活性组分并与其形成更加稳固的结构,以保证在发挥催化作用的同时不会脱落造成损失,提高经济性。热敏性配体能够及时对反应过程中生成的离子态活性组分进行转化,使其还原为单质态活性组分,迅速重新发挥催化作用。
本发明所述醋酸烯丙酯催化剂,各组分具有合适的位置分布和良好的活性,能够减少活性组分用量和损失,提高催化剂整体导热性和扩散性能,具有组成分散均匀牢固,强度高,耐温性能好,导热性能好,时空收率高,产品选择性高,稳定性好,催化剂寿命长等优点,适用于醋酸、氧气和丙烯合成醋酸烯丙酯,提高经济性。
附图说明
图1为实施例1制备的催化剂的结构图;
图2为对比例1制备的催化剂的结构图;
图3为实施例1催化剂的活性组分分布图;
图4为对比例1催化剂的活性组分分布图。
具体实施方式
为了更好地说明本发明,下面结合具体实施方式进一步说明本发明。但本发明的范围不只限于这些实施例的范围。
本发明实施例和对比例中使用的主要原料来源信息如下,其它试剂原料如无特别说明,均为普通市售产品:
碳化硅球:平均粒径2.0mm,比表面积250.5m2/g,孔容0.45cm3/g,平均孔径15.0mm,工业级,上海乃欧纳米科技有限公司;
碳化硅棒:平均粒径2.4mm,比表面积249.6m2/g,孔容0.45cm3/g,平均孔径15.0mm,工业级,上海乃欧纳米科技有限公司;
碳化硅环:平均粒径2.3mm,比表面积231.0m2/g,孔容0.45cm3/g,平均孔径15.0mm,工业级,上海乃欧纳米科技有限公司;
硅胶球:平均粒径2.0mm,比表面积240.0m2/g,孔容0.45cm3/g,平均孔径15.0mm,工业级,格雷斯特种化学品和材料公司;
石墨烯小球:平均粒径2.1mm,比表面积249.8m2/g,孔容0.45cm3/g,平均孔径14.9mm,工业级,恒力盛泰(厦门)石墨烯科技有限公司。
本发明实施例或对比例中所用的计算方法和测试方法如下:
1、使用气相色谱法(色谱仪为Agilent GC 8890A)分析反应产物中各组分的含量,并按下列公式计算催化剂的活性和选择性:
催化剂活性(目标产物时空收率)=生成醋酸烯丙酯的量/催化剂体积/反应时间,单位为gAAC/LCat./h;
选择性=(生成醋酸烯丙酯的量/反应消耗丙烯的量)×100%;
关于催化剂的使用寿命,以催化剂的活性(STY值)为300gAAC/Lcat./h计,STY值低于300,一般认为催化剂活性未满足工业化使用要求。
2、比表面积和孔结构信息的测定方法
比表面积、孔容、孔径采用低温液氮物理吸收法,样品的比表面积依据BET理论进行计算,孔容和孔径分布通过t-plot BJH模型进行计算,测试仪器型号为MicromeriticsASAP 2460。
3、颗粒强度的测定方法
颗粒强度采用压力测定法,检测依据为GB102012-88,测试仪器型号为FT-803。
4、导热性能测定方法
导热系数采用非稳态导热测试法,检测依据为GB/T10297-2015测试仪器型号为KEM QTM-500。
5、催化剂活性组分分布
活性组分分布采用SEM-EDS进行测定,采用JEOL扫描电子显微镜观察放大到微米尺度的分布情况。
实施例1
制备醋酸烯丙酯催化剂,步骤为:
(1)配制500g含有13.8g氯钯酸钠(其中Pd 5.0g,0.05mol)和10.6g氯化铜(其中Cu5.0g,0.08mol)的混合水溶液,向其中加入500g碳化硅球以及5.0g异丙基丙烯酰胺,在20℃下进行配位反应20h,反应完成后加入浓度为10wt%的硅酸钠(其中Na2SiO315.9g,0.13mol)水溶液,在20℃下沉淀反应20h,得到含前驱体A的反应液。
(2)向含前驱体A的反应液中加入6.3g(0.13mol)水合肼混合均匀,20℃下还原10h后,采用40℃温水洗涤至滤液中无氯离子,洗涤完成后在120℃下干燥5h,得到前驱体B。
(3)将515.0g前驱体B加入到225.7g浓度为10wt%的醋酸钾水溶液中,在20℃下混合浸渍10h,120℃干燥5h,得到成品催化剂1。
催化剂1结构如图1所示,具有“蜂窝状”结构,内部组分呈“外多内少”分布,所述活性组分自壳层每向内延伸10μm,活性组分浓度降低减少10wt%(活性组分分布如图3),导热系数如表1所示。
催化剂1中,基于载体质量计,活性组分Pd负载量为1.0wt%,活性组分Cu负载量为1.0wt%,配体异丙基丙烯酰胺负载量为1.0wt%,助活性组分醋酸钾负载量为1.8wt%。
催化剂1粒径为2.6mm,比表面积为298m2/g,孔容为0.35cm3/g,孔径为13.5nm。
催化剂性能评价:
制备醋酸烯丙酯,步骤为:将500mL催化剂1放入内径40mm,高度2000mm的固定床反应器中,上下两端装填有惰性瓷球,进料组成为丙烯:氧气:醋酸:水的摩尔比为1:0.3:0.6:0.4,反应温度140℃,反应压力0.75MPaG,反应体积空速1800h-1,反应后的产品经过冷凝后进行色谱分析,评价结果如表1所示。
实施例2
制备醋酸烯丙酯催化剂,步骤为:
(1)配制500g含有69.0g氯钯酸钠(其中Pd 25.0g,0.23mol)和31.7g氯化铜(其中Cu 15.0g,0.24mol)的混合水溶液,向其中加入500g碳化硅球以及50.0g异丙基丙烯酰胺,在30℃下进行配位反应20h,反应完成后加入浓度为10wt%的硅酸钠(其中Na2SiO3 61.1g,0.50mol)水溶液中,在20℃下沉淀反应20h得到前驱体A。
(2)向含前驱体A的反应液中加入66.1g(1.32mol)水合肼混合均匀,20℃下还原10h后,采用40℃温水洗涤至滤液中无氯离子,洗涤完成后在120℃下干燥5h,得到前驱体B。
(3)将590.0g前驱体B加入到376.1g浓度为10wt%的醋酸钾水溶液中,在20℃下混合浸渍20h,120℃干燥5h,得到成品催化剂2。
催化剂2具有“蜂窝状”结构,内部组分呈“外多内少”分布,所述活性组分自壳层每向内延伸10μm,活性组分浓度降低减少13wt%,导热系数如表1所示。
催化剂2中,基于载体质量计,活性组分Pd负载量为5.0wt%,活性组分Cu负载量为3.0wt%,配体异丙基丙烯酰胺负载量为10.0wt%,助活性组分醋酸钾负载量为3.0wt%。
催化剂2粒径为2.9mm,比表面积为325m2/g,孔容为0.42cm3/g,孔径为14.0nm。
催化剂性能评价:
制备醋酸烯丙酯,步骤为:将500mL催化剂1放入内径40mm,高度2000mm的固定床反应器中,上下两端装填有惰性瓷球,进料组成为丙烯:氧气:醋酸:水的摩尔比为1:0.4:0.6:0.5,反应温度140℃,反应压力0.65MPaG,反应体积空速1800h-1,反应后的产品经过冷凝后进行色谱分析,评价结果如表1所示。
实施例3
制备醋酸烯丙酯催化剂,步骤为:
(1)配制500g含有27.6g氯钯酸钠(其中Pd 10.0g,0.09mol)和69.0g氯金酸(其中Au 40.0g,0.20mol)的混合水溶液,向其中加入500g碳化硅环以及25.0g三联吡啶氯化钠,在25℃下进行配位反应40h,反应完成后加入浓度为10wt%的碳酸钠(其中Na2CO3 30.7g,0.29mol)水溶液中,在20℃下沉淀反应20h得到前驱体A。
(2)向含前驱体A的反应液中加入66.1g(1.32mol)水合肼混合均匀,20℃下还原10h后,采用40℃温水洗涤至滤液中无氯离子,洗涤完成后在120℃下干燥5h,得到前驱体B。
(3)将575.0g前驱体B加入到125.4g浓度为10wt%的醋酸钾水溶液中,在20℃下混合浸渍20h,120℃干燥5h,得到成品催化剂3。
催化剂3具有“蜂窝状”结构,内部组分呈“外多内少”分布,所述活性组分自壳层每向内延伸10μm,活性组分浓度降低减少12wt%,导热系数如表1所示。
催化剂3中,基于载体质量计,活性组分Pd负载量为2.0wt%,活性组分Au负载量为8.0wt%,配体三联吡啶氯化钠负载量为5.0wt%,助活性组分醋酸钾负载量为1.0wt%。
催化剂3粒径为2.5mm,比表面积为280m2/g,孔容为0.38cm3/g,孔径为12.8nm。
催化剂性能评价:
制备醋酸烯丙酯,步骤为:将500mL催化剂1放入内径40mm,高度2000mm的固定床反应器中,上下两端装填有惰性瓷球,进料组成为丙烯:氧气:醋酸:水的摩尔比为1:0.5:0.5:0.5,反应温度140℃,反应压力0.85MPaG,反应体积空速1800h-1,反应后的产品经过冷凝后进行色谱分析,评价结果如表1所示。
实施例4
制备醋酸烯丙酯催化剂,步骤为:
(1)配制500g含有31.7g氯化铜(其中Cu 15.0g,0.24mol)和69.0g氯金酸(其中Au35.0g,0.18mol)的混合水溶液,向其中加入500g碳化硅环以及25.0g(4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]钠,在30℃下进行配位反应20h,反应完成后加入浓度为10wt%的氢氧化钠(其中NaOH 84.1g,2.10mol)水溶液中,在20℃下沉淀反应40h得到前驱体A。
(2)向含前驱体A的反应液中加入66.1g(1.32mol)水合肼混合均匀,20℃下还原10h后,采用40℃温水洗涤至滤液中无氯离子,洗涤完成后在120℃下干燥5h,得到前驱体B。
(3)将575.0g前驱体B加入到125.4g浓度为10wt%的醋酸钾水溶液中,在20℃下混合浸渍20h,120℃干燥5h,得到成品催化剂3。
催化剂4具有“蜂窝状”结构,内部组分呈“外多内少”分布,所述活性组分自壳层每向内延伸10μm,活性组分浓度降低减少11wt%,导热系数如表1所示。
催化剂4中,基于载体质量计,活性组分Cu负载量为3.0wt%,活性组分Au负载量为7.0wt%,配体(4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]钠负载量为5.0wt%,助活性组分醋酸钾负载量为1.0wt%。
催化剂4粒径为2.8mm,比表面积为310m2/g,孔容为0.39cm3/g,孔径为14.1nm。
催化剂性能评价:
制备醋酸烯丙酯,步骤为:将500mL催化剂1放入内径40mm,高度2000mm的固定床反应器中,上下两端装填有惰性瓷球,进料组成为丙烯:氧气:醋酸:水的摩尔比为1:0.7:0.8:0.9,反应温度140℃,反应压力0.75MPaG,反应体积空速1800h-1,反应后的产品经过冷凝后进行色谱分析,评价结果如表1所示。
实施例5
制备醋酸烯丙酯催化剂,步骤为:
(1)配制500g含有27.6g氯钯酸钠(其中Pd 10.0g,0.09mol)和69.0g氯金酸(其中Au 40.0g,0.20mol)的混合水溶液,向其中加入500g碳化硅棒以及25.0g热敏水凝胶,在25℃下进行配位反应40h,反应完成后加入浓度为10wt%的碳酸钠(其中Na2CO3 30.7g,0.29mol)水溶液中,在20℃下沉淀反应20h得到前驱体A。
(2)向含前驱体A的反应液中按照气速为1L/min通入体积浓度为5vol%的氢气(0.002mol/min),20℃下继续还原10h,得到前驱体B。
(3)将575.0g前驱体B加入到125.4g浓度为10wt%的醋酸钾水溶液中,在20℃下混合浸渍20h,120℃干燥5h,得到成品催化剂5。
催化剂5具有“蜂窝状”结构,内部组分呈“外多内少”分布,所述活性组分自壳层每向内延伸10μm,活性组分浓度降低减少20wt%,导热系数如表1所示。
催化剂5中,基于载体质量计,活性组分Pd负载量为2.0wt%,活性组分Au负载量为8.0wt%,配体热敏水凝胶负载量为5.0wt%,助活性组分醋酸钾负载量为1.0wt%。
催化剂5粒径为2.9mm,比表面积为301m2/g,孔容为0.36cm3/g,孔径为13.1nm。
催化剂性能评价:
制备醋酸烯丙酯,步骤为:将500mL催化剂1放入内径40mm,高度2000mm的固定床反应器中,上下两端装填有惰性瓷球,进料组成为丙烯:氧气:醋酸:水的摩尔比为1:0.8:0.6:0.7,反应温度140℃,反应压力0.70MPaG,反应体积空速1800h-1,反应后的产品经过冷凝后进行色谱分析,评价结果如表1所示。
对比例1
参照实施例1方法制备醋酸烯丙酯催化剂,不同之处仅在于:步骤(1)中碳化硅球换成硅胶球,其他操作和条件不变,制得催化剂(结构如图2、活性组分分布如图4)),性能评价结果如表1所示。
对比例2
参照实施例1方法制备醋酸烯丙酯催化剂,不同之处仅在于:步骤(1)中碳化硅球换成石墨烯小球,其他操作和条件不变,制得催化剂,性能评价结果如表1所示。
对比例3
参照实施例1方法制备醋酸烯丙酯催化剂,不同之处仅在于:步骤(1)中醋酸钾换成醋酸镁,其他操作和条件不变,制得催化剂,性能评价结果如表1所示。
对比例4
参照实施例1方法制备醋酸烯丙酯催化剂,不同之处仅在于:步骤(1)中醋酸钾换成硝酸钾,其他操作和条件不变,制得催化剂,性能评价结果如表1所示。
对比例5
参照实施例1方法制备醋酸烯丙酯催化剂,不同之处仅在于:步骤(2)中不加入配体,其他操作和条件不变,制得催化剂,性能评价结果如表1所示。
对比例6
参照实施例1方法制备醋酸烯丙酯催化剂,不同之处仅在于:步骤(2)中配体换成三苯基膦,其他操作和条件不变,制得催化剂,性能评价结果如表1所示。
表1不同催化剂初始活性及寿命评价结果
由图1的数据可以看出,本发明方法将含活性组分金属盐配制成溶液同配体进行配位后同载体进行混合并进行负载,经过沉淀和还原后,将助剂金属盐配成溶液进行沉淀浸渍制得一种整体呈“蜂窝状”结构,内部组分呈“外多内少”分布的醋酸烯丙酯催化剂。
从表1的数据可以看到,本发明制备的催化剂具有组成均匀牢固锚定,活性组分分散度高,导热性能好,时空收率高,产品选择性高,稳定性好等特点,适用于醋酸、氧气和丙烯合成醋酸烯丙酯。
Claims (10)
1.一种负载型醋酸烯丙酯催化剂,其特征在于,所述催化剂含有载体,以及载体上负载的活性组分、配体、助活性组分;
所述载体为碳化硅材料;
所述活性组分选自金属Pd、Au、Cu中的至少一种;
所述助活性组分选自碱金属醋酸盐中的至少一种,优选为醋酸钠和/或醋酸钾;
所述配体选自异丙基丙烯酰胺、(4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]钠、三联吡啶氯化钠、紫杉醇、热敏水凝胶中的至少一种。
2.根据权利要求1所述的负载型醋酸烯丙酯催化剂,其特征在于,所述载体为碳化硅材料,选自碳化硅球、碳化硅棒和碳化硅环中的至少一种,更优选为碳化硅球;
所述碳化硅材料,粒径为1~5mm,优选2~3mm;
所述活性组分负载量为0.1~10.0wt%,优选1~10.0wt%,基于载体质量计;
所述助活性组分负载量为1.0~10.0wt%,优选1.0~5.0wt%,基于载体质量计;
所述配体负载量为0.05~20.0wt%,优选0.1~10.0wt%,基于载体质量计。
3.根据权利要求1或2所述的负载型醋酸烯丙酯催化剂,其特征在于,所述醋酸烯丙酯催化剂,粒径为1~5mm,优选2~3mm;比表面积为50~800m2/g,优选200~600m2/g;孔容为0.2~1.0cm3/g,优选0.2~0.6cm3/g;孔径为5~20nm,优选10~15nm;
所述醋酸烯丙酯催化剂,具有“蜂窝状”结构,内部组分呈“外多内少”分布,优选地,所述活性组分自壳层每向内延伸10μm,活性组分浓度降低10~20wt%。
4.一种权利要求1-3任一项所述的负载型醋酸烯丙酯催化剂的制备方法,其特征在于,步骤包括:
(1)将含活性组分的金属盐配制成溶液,然后加入载体和配体进行配位反应,再加入沉淀剂进行沉淀反应,得到含前驱体A的反应液;
(2)向步骤(1)的反应液中加入还原剂进行还原反应,再经洗涤、干燥,得到前驱体B;
(3)将步骤(2)的前驱体B加入到含助活性组分的溶液中浸渍,取出后干燥,得到负载型醋酸烯丙酯催化剂。
5.根据权利要求4所述的负载型醋酸烯丙酯催化剂的制备方法,其特征在于,步骤(1)中,所述含活性组分的金属盐溶液为水溶液,浓度为5~30wt%,优选10~20wt%;
所述含活性组分的金属盐选自Pd、Au、Cu的氯化盐、硝酸盐、醋酸盐中的至少一种,优选Pd、Au和Cu的氯化盐中的至少一种;
步骤(1)中,所述载体选自碳化硅材料,优选碳化硅球、碳化硅棒和碳化硅环中的至少一种,更优选为碳化硅球;
所述碳化硅材料,粒径为1~5mm,优选2~3mm;
步骤(1)中,所述含活性组分的金属盐溶液,以其中的金属盐计,与载体混合的质量比为1:1~100,优选1:2~50;
步骤(1)中,所述配体选自异丙基丙烯酰胺、(4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]钠、三联吡啶氯化钠、紫杉醇、热敏水凝胶中的至少一种,优选为异丙基丙烯酰胺;
所述配体与载体的质量比为1:5~200,优选1:10~100;
步骤(1)中,所述沉淀剂选自氢氧化钾、氢氧化钠、碳酸钾、碳酸钠、硅酸钾、硅酸钠中的至少一种,优选为氢氧化钠、硅酸钠、碳酸钠中的至少一种;
所述沉淀剂用量,为含活性组分的金属盐溶液中金属摩尔量的1~20倍,优选1~5倍;
优选地,所述沉淀剂配制为水溶液使用,浓度为1~20wt%,优选5~10wt%。
6.根据权利要求4或5所述的制备方法,其特征在于,步骤(1)中,所述配位反应,温度为10~50℃,优选20~30℃;时间为10~72h,优选20~40h;
步骤(1)中,步骤(1)中,所述沉淀反应,温度为10~50℃,优选20~30℃;时间为10~72h,优选20~40h。
7.根据权利要求4-6任一项所述的制备方法,其特征在于,步骤(2)中,所述还原剂选自乙烯、丙烯、氢气、水合肼、甲醛中的至少一种,优选为氢气、丙烯、水合肼中的至少一种;
所述还原剂的加入量,为步骤(1)中含活性组分的金属盐溶液中金属摩尔量的0.5~20倍,优选1~15倍;
步骤(2)中,所述还原反应,温度为10~50℃,优选20~30℃;时间为5~40h,优选10~20h;
步骤(2)中,所述干燥温度为100~150℃;干燥时间为2~10h。
8.根据权利要求4-7任一项所述的制备方法,其特征在于,步骤(3)中,所述含助活性组分的溶液为水溶液,浓度为1~20wt%,优选5~10wt%;
所述助活性组分选自碱金属醋酸盐中的至少一种,优选为醋酸钾;
所述前驱体B与含助活性组分的溶液的质量比为1:0.1~20,优选1:0.2~10;
步骤(3)中,所述浸渍,温度为10~50℃,时间为5~36h;
步骤(3)中,所述干燥,温度为100~150℃,时间为2~10h。
9.权利要求1-3任一项所述的负载型醋酸烯丙酯催化剂或者由权利要求6-8任一项所述方法制备的负载型醋酸烯丙酯催化剂在醋酸烯丙酯制备中的应用。
10.一种醋酸烯丙酯的制备方法,其特征在于步骤包括:采用固定床反应器,在权利要求1-3任一项所述的负载型醋酸烯丙酯催化剂或者由权利要求6-8任一项所述方法制备的负载型醋酸烯丙酯催化剂的存在下,将丙烯、氧气、醋酸、水混合进行反应制备醋酸烯丙酯;
所述丙烯与氧气、醋酸、水的摩尔比1:0.3~1:0.2~1:0.3~1;
所述反应,温度为120~180℃,优选140~170℃;压力为0.6~0.9MPaG,优选0.65~0.85MPaG;反应体积空速为1500~2500h-1,优选1800~2000h-1。
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