CN115025807A - 用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂及其制备方法与应用 - Google Patents
用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂及其制备方法与应用 Download PDFInfo
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- CN115025807A CN115025807A CN202210958069.XA CN202210958069A CN115025807A CN 115025807 A CN115025807 A CN 115025807A CN 202210958069 A CN202210958069 A CN 202210958069A CN 115025807 A CN115025807 A CN 115025807A
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- molecular sieve
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- dimethylaminoethyl methacrylate
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 86
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 18
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960002887 deanol Drugs 0.000 claims abstract description 16
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 30
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 20
- 238000005809 transesterification reaction Methods 0.000 claims description 17
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 11
- 238000000066 reactive distillation Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000002148 esters Chemical group 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- ZMVHTLOQSTVDFE-UHFFFAOYSA-N methanol;methyl 2-methylprop-2-enoate Chemical compound OC.COC(=O)C(C)=C ZMVHTLOQSTVDFE-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000009738 saturating Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 49
- 239000000047 product Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000007036 catalytic synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- UYHNDEQBDLNIJY-UHFFFAOYSA-N 2,2-diaminoethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(N)N UYHNDEQBDLNIJY-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 paper-making aids Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- 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 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ZDTVBVUHESZSGN-UHFFFAOYSA-N 1,1-diaminoethanol Chemical compound CC(N)(N)O ZDTVBVUHESZSGN-UHFFFAOYSA-N 0.000 description 1
- GANGMFBTSGBBRL-UHFFFAOYSA-N 2-(dimethylamino)-2-hydroxyacetic acid Chemical compound CN(C)C(O)C(O)=O GANGMFBTSGBBRL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- QAZYYQMPRQKMAC-FDGPNNRMSA-L calcium;(z)-4-oxopent-2-en-2-olate Chemical compound [Ca+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QAZYYQMPRQKMAC-FDGPNNRMSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 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 1
- 150000003751 zinc Chemical class 0.000 description 1
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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Abstract
本发明属于绿色催化精细化工技术领域,具体涉及一种用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂及其制备方法与应用。该分子筛催化剂为Na2O‑CaO‑MgO‑V2O5/LaY,其中Na2O:CaO:MgO:V2O5的质量比为1:1.9‑2.1:2.0‑2.2:1,LaY中La含量为7‑10wt.%;Na2O‑CaO‑MgO‑V2O5的总质量为LaY质量的25‑35%。本发明将Na2O‑CaO‑MgO‑V2O5/LaY分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,催化效率高,且反应产率较高,甲基丙烯酸二甲基氨基乙酯的纯度≥99%。
Description
技术领域
本发明属于绿色催化精细化工技术领域,具体涉及一种用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂及其制备方法与应用。
背景技术
甲基丙烯酸二甲基氨基乙酯是重要的甲基丙烯酸特种酯之一,由于其分子内同时含有活泼的双键和碱性叔胺基等活性基团,使其具有较强的反应活性,可进行均聚、共聚、季铵化为主的各种化学反应,合成具有活性胺基或季胺基的高分子化合物,在水处理剂、造纸助剂、纤维工业、塑料橡胶工业、涂料工业、印刷材料、医药医疗、石油添加剂、粘合剂、化妆品、洗涤剂和表面活性剂等领域具有广泛的应用,也是生产阳离子型和两性离子型聚合物的重要原料之一。
甲基丙烯酸二甲基氨基乙酯的合成方法主要有直接酯化法和酯交换法。直接酯化法是用甲基丙烯酸和二甲氨基乙醇酸直接反应生成甲基丙烯酸二甲基氨基乙酯,并副产水。该工艺为传统的酯化方法,催化剂可用硫酸或对甲苯磺酸,工艺简单,但由于目前工业上多以甲基丙烯醛、甲醇和氧气直接氧化酯化合成甲基丙烯酸甲酯,直接生产甲基丙烯酸的厂家很少,且甲基丙烯酸自身气味大、不宜储存,从而限制了直接酯化法的推广。酯交换法是目前常用的技术路线,采用甲基丙烯酸甲酯和二氨基乙醇酯交换合成甲基丙烯酸二甲基氨基乙酯。
中国专利CN102850155A和CN101486648A公开了甲基丙烯酸酯类产品的制备方法。该技术采用两个反应釜串联的反应装置,以甲基丙烯酸甲酯和醇为原料,辅以催化剂和阻聚剂,置于反应釜中加热反应,生成甲基丙烯酸酯类产品和甲醇。但该工艺需以有机锡、钛酸酯复配作为催化剂,且工艺是间歇式酯交换反应。吴殿义等采用钛酸四丁酯催化间歇酯交换合成甲基丙烯酸二甲氨基乙酯,收率97.99%(大庆石油学院学报, 2003, 27, 2, 34-36)。张光旭等采用钛酸异丙酯催化间歇酯交换合成甲基丙烯酸二甲氨基乙酯,收率90%左右(精细化工, 2008, 37, 11, 1160-1165)。刘福生等人采用了多种锌盐、钾盐、金属氧化物、醋酸盐、碳酸盐和醇钾等作为催化剂催化间歇酯交换合成甲基丙烯酸二甲氨基乙酯,转化率在71.2-98.8%,但反应副产杂质问题突出(齐鲁石油化工, 1994, 2, 122-126)。黄文平等以二丁基氧化锡催化间歇酯交换合成甲基丙烯酸二甲氨基乙酯,收率90.2%,纯度97.3%(咸宁师专学报, 2002, 22, 3, 61-62)。刘祥臣等以二丁基月桂酸锡催化间歇酯交换合成甲基丙烯酸二甲氨基乙酯,反应转化率93%(化学世界, 2002, 3, 138-140)。此外还有部分学者以铅、钠、钙、乙酰丙酮钙、碱金属氧化物或氢氧化物、碱金属磷酸盐或碳酸盐、异丙醇铝和钛酸钾等进行催化间歇式酯交换。
上述已公开专利或期刊报道的技术均存在间歇式操作,催化剂单次使用、催化剂和体系难分离、副产物多以及反应收率高低不同等一系列制约行业发展的关键瓶颈问题,因此急需开发一种高效固体催化剂以实现高效连续酯交换反应。
发明内容
本发明的目的是提供一种用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂,该催化剂具有酸碱、阻聚和抗烧结多活性中心,催化效率高;本发明同时提供其制备方法与应用。
本发明解决其技术问题所采取的技术方案是:
本发明所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂,该分子筛催化剂为Na2O-CaO-MgO-V2O5/LaY,其中Na2O:CaO:MgO:V2O5的质量比为1:1.9-2.1:2.0-2.2:1,LaY中La含量为7-10wt.%;Na2O-CaO-MgO-V2O5/LaY中Na2O-CaO-MgO-V2O5的总质量为LaY质量的25-35%。
所述的Na2O-CaO-MgO-V2O5/LaY分子筛催化剂的颗粒直径为3-4mm,长度为5-7mm。
本发明所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的制备方法,包括以下步骤:
(1)将NaY分子筛制成浆液,加入硝酸镧溶液进行离子交换,得到混合浆液;
(2)向步骤(1)得到的混合浆液中加入表面活性剂,同时加入硝酸镁与硝酸钙混合水溶液、氨水进行共沉淀,经老化、烘干、焙烧得到Na2O-CaO-MgO/LaY分子筛;
(3)将步骤(2)得到的Na2O-CaO-MgO/LaY分子筛于偏钒酸铵溶液中浸渍,再经烘干、焙烧得到Na2O-CaO-MgO-V2O5/LaY分子筛催化剂。
其中:
步骤(1)为:将NaY分子筛制成质量分数20-25%的浆液,超声30-35min后升温至70-80℃,再加入25-35wt.%的硝酸镧溶液进行离子交换2-4h,得到混合浆液;所述的硝酸镧溶液中硝酸镧与NaY分子筛的质量比0.07-0.1:1。
所述的NaY分子筛中SiO2: Al2O3的摩尔比为5,Na2O含量为 13wt.%。
NaY分子筛与表面活性剂、硝酸镁与硝酸钙混合水溶液中溶质、氨水中溶质(NH3)的质量比为100:2:170-175:35-40;所述的硝酸镁与硝酸钙混合水溶液的浓度为20-30wt.%,其中硝酸镁与硝酸钙的质量比为1.26:1;所述的氨水的浓度为10-15wt.%。
步骤(2)中,所述的表面活性剂为羟甲基纤维素、羟乙基纤维素、聚丙烯酰胺或聚乙二醇600;共沉淀时间为60-90min,共沉淀温度为70-80℃;老化时间为3-5h;焙烧温度为500-550℃。
步骤(3)中,50-60℃下,将步骤(2)得到的Na2O-CaO-MgO/LaY分子筛于偏钒酸铵溶液中饱和浸渍3-3.5h;所述的焙烧温度为450-500℃。
本发明所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的应用:以甲基丙烯酸甲酯和二甲基氨基乙醇为原料经混合后连续化进入反应精馏塔,反应精馏塔中装填Na2O-CaO-MgO-V2O5/LaY分子筛催化剂,在反应精馏塔中进行连续化催化酯交换反应,塔顶连续化采出甲醇-甲基丙烯酸甲酯共沸物,塔釜连续化采出粗产品,经精馏得到甲基丙烯酸二甲基氨基乙酯产品。
其中:
所述的甲基丙烯酸甲酯与二甲基氨基乙醇的摩尔比为2-4:1,优选3-4:1。
所述的连续化催化酯交换反应的温度为100-120℃,优选100-110℃;压力为0.3-0.8MPa,优选0.3-0.5MPa。
所述的反应精馏塔塔顶的摩尔回流比为8-12,连续化催化酯交换反应的质量空速范围为0.8-1.2g/(g·h),优选0.8-1.0g/(g·h)。
本发明的有益效果如下:
本发明Na2O-CaO-MgO-V2O5/LaY分子筛催化剂的制备过程中,NaY分子筛制成浆液,加入硝酸镧溶液进行离子交换,离子交换后的Na+不需要脱除而是与溶液中的NO3 -形成硝酸钠,以硝酸钠的形式留在分子筛表面及孔道,克服了传统离子交换过程中副产大量高盐废水,创造性的将交换后的盐变成催化剂的活性成分;硝酸镁与硝酸钙一起进行共沉淀,生成氢氧化镁和氢氧化钙均匀沉积到分子筛上,在焙烧过程中可进行固体交换,进入分子筛孔道中,得到Na2O-CaO-MgO/LaY分子筛。最后将Na2O-CaO-MgO/LaY分子筛于偏钒酸铵溶液中饱和浸渍,经烘干、焙烧,在Na2O-CaO-MgO/LaY分子筛催化剂表面形成高度分散的V2O5活性物,形成Na2O-CaO-MgO-V2O5/LaY分子筛催化剂,与La元素协同可有效防止原料和产物聚合。本发明整个催化剂制备过程无废水排放,工艺绿色环保,原子利用率高。
本发明得到的Na2O-CaO-MgO-V2O5/LaY分子筛催化剂是一种具有酸碱、阻聚和抗烧结多活性中心的固体催化剂,其中Na2O-CaO-MgO提供碱性位,V2O5和La协同提供阻聚作用,LaY提供酸性活性中心。本发明将Na2O-CaO-MgO-V2O5/LaY分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,酸碱多活性中心强化酯交换反应过程以提高反应速率,延长催化剂寿命,减少原料和目标产物的聚合;V2O5-La协同能有效减缓原料和产物在催化剂表面的聚合程度,同时稀土元素La提高催化剂的催化活性和使用寿命,催化效率高,反应产率较高,且甲基丙烯酸二甲基氨基乙酯的纯度≥99%。另外,本发明催化反应耦合了反应和精馏之间的协同作用,强化物料之间的传质与传热,提高了单位时间内的生产效率,实现了节能环保的连续化工艺。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
Na2O-CaO-MgO-V2O5/LaY分子筛催化剂的制备包括以下步骤:
(1)将100g NaY分子筛(SiO2: Al2O3的摩尔比为5,Na2O含量为13wt.%)置于水中制成质量分数20%浆液,超声30min后升温至70℃,加入30g浓度 30wt.%的硝酸镧溶液进行离子交换3h,得到混合浆液;
(2)向步骤(1)得到的混合浆液中加入2g羟甲基纤维素,同时加入850.05g浓度为20wt.%的硝酸镁与硝酸钙混合水溶液(其中硝酸镁与硝酸钙的质量比为1.26:1)、400.09g浓度为10wt.%的氨水,于70℃下进行共沉淀90min,经老化3h、烘干、500℃下焙烧1h得到Na2O-CaO-MgO/LaY分子筛;
(3)将步骤(2)得到的Na2O-CaO-MgO/LaY分子筛饱和浸渍于偏钒酸铵溶液中,55℃超声浸渍3h,再经烘干、480℃下焙烧1.5h,得到Na2O-CaO-MgO-V2O5/LaY分子筛催化剂;该催化剂中Na2O:CaO:MgO:V2O5的质量比为1:1.9:2:1,所述LaY中La含量为9wt.%;所述Na2O-CaO-MgO-V2O5的总质量为LaY质量的25%。
将上述得到的Na2O-CaO-MgO-V2O5/LaY分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,具体过程如下:
以300.36g甲基丙烯酸甲酯和89.14g二甲基氨基乙醇为原料经混合后连续化加入反应精馏塔中,反应精馏塔中装填30g Na2O-CaO-MgO-V2O5/LaY分子筛催化剂,温度100℃,压力0.5MPa下进行连续化催化酯交换反应,连续化催化酯交换反应的质量空速为1.0g/(g·h),反应精馏塔塔顶的摩尔回流比为8;塔顶连续化采出甲醇-甲基丙烯酸甲酯共沸物,塔釜连续化采出甲基丙烯酸二氨基乙酯粗产品,经精馏得到甲基丙烯酸二甲基氨基乙酯产品154.69g,收率为98%,纯度99.6%。该催化剂使用6个月时,其催化合成得到的甲基丙烯酸二甲基氨基乙酯的收率为96.5%。
实施例2
Na2O-CaO-MgO-V2O5/LaY分子筛催化剂的制备包括以下步骤:
(1)将100g NaY分子筛(SiO2: Al2O3的摩尔比为5,Na2O含量为13wt.%)置于水中制成质量分数20%浆液,超声35min后升温至75℃,加入20g 浓度35wt.%的硝酸镧溶液进行离子交换4h,得到混合浆液;
(2)向步骤(1)得到的混合浆液中加入2g聚丙烯酰胺,同时加入689.36g浓度为25wt.%的硝酸镁与硝酸钙混合水溶液(其中硝酸镁与硝酸钙的质量比为1.26:1)、252.7g浓度为15wt.%的氨水,于80℃下进行共沉淀60min,经老化4h、烘干、550℃下焙烧1h得到Na2O-CaO-MgO/LaY分子筛;
(3)将步骤(2)得到的Na2O-CaO-MgO/LaY分子筛饱和浸渍于偏钒酸铵溶液中,50℃超声浸渍3.5h,再经烘干、450℃下焙烧1.5h,得到Na2O-CaO-MgO-V2O5/LaY分子筛催化剂;该催化剂中Na2O:CaO:MgO:V2O5的质量比为1:2:2.1:1,所述LaY中La含量为7wt.%;所述Na2O-CaO-MgO-V2O5的总质量为LaY质量的35%。
将上述得到的Na2O-CaO-MgO-V2O5/LaY分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,具体过程如下:
以400.48g甲基丙烯酸甲酯和178.28g二甲基氨基乙醇为原料经混合后连续化加入反应精馏塔中,反应精馏塔中装填40g Na2O-CaO-MgO-V2O5/LaY分子筛催化剂,温度110℃,压力0.3MPa下进行连续化催化酯交换反应,连续化催化酯交换反应的质量空速为0.8g/(g·h),反应精馏塔塔顶的摩尔回流比为10;塔顶连续化采出甲醇-甲基丙烯酸甲酯共沸物,塔釜连续化采出甲基丙烯酸二氨基乙酯粗产品,经精馏得到甲基丙烯酸二甲基氨基乙酯产品310.64g,收率为98.5%,纯度99.7%。该催化剂使用6个月时,其催化合成得到的甲基丙烯酸二甲基氨基乙酯的收率为96.8%。
实施例3
Na2O-CaO-MgO-V2O5/LaY分子筛催化剂的制备包括以下步骤:
(1)将100g NaY分子筛(SiO2: Al2O3的摩尔比为5,Na2O含量为13wt.%)置于水中制成质量分数20%浆液,超声32min后升温至80℃,加入40g浓度25wt.%的硝酸镧溶液进行离子交换2h,得到混合浆液;
(2)向步骤(1)得到的混合浆液中加入2g聚乙二醇600,同时加入583.34g浓度为30wt.%的硝酸镁与硝酸钙混合水溶液(其中硝酸镁与硝酸钙的质量比为1.26:1)、291.84g浓度为12wt.%的氨水,于75℃下进行共沉淀75min,经老化5h、烘干、530℃下焙烧1.5h得到Na2O-CaO-MgO/LaY分子筛;
(3)将步骤(2)得到的Na2O-CaO-MgO/LaY分子筛饱和浸渍于偏钒酸铵溶液中,60℃超声浸渍3.2h,再经烘干、500℃下焙烧1h,得到Na2O-CaO-MgO-V2O5/LaY分子筛催化剂;该催化剂中Na2O:CaO:MgO:V2O5的质量比为1:2.1:2.2:1,所述LaY中La含量为10wt.%;所述Na2O-CaO-MgO-V2O5的总质量为LaY质量的30%。
将上述得到的Na2O-CaO-MgO-V2O5/LaY分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,具体过程如下:
以898.5g甲基丙烯酸甲酯和200g二甲基氨基乙醇为原料经混合后连续化加入反应精馏塔中,反应精馏塔中装填90g Na2O-CaO-MgO-V2O5/LaY分子筛催化剂,温度120℃,压力0.8MPa下进行连续化催化酯交换反应,连续化催化酯交换反应的质量空速为1.2g/(g·h),反应精馏塔塔顶的摩尔回流比为12;塔顶连续化采出甲醇-甲基丙烯酸甲酯共沸物,塔釜连续化采出甲基丙烯酸二氨基乙酯粗产品,经精馏得到甲基丙烯酸二甲基氨基乙酯产品348.84g,收率为98.7%,纯度99.8%。该催化剂使用6个月时,其催化合成得到的甲基丙烯酸二甲基氨基乙酯的收率为97.1%。
对比例1
在分子筛催化剂的制备过程中不进行步骤(3),其余步骤同实施例1。
将得到的Na2O-CaO-MgO/LaY分子筛用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,步骤同实施例1。得到甲基丙烯酸二甲基氨基乙酯产品145.34g,收率为87.0%,纯度94.1%。该催化剂使用1个月时,其催化合成得到的甲基丙烯酸二甲基氨基乙酯的收率为82.7%。
对比例2
在分子筛催化剂的制备过程中不进行步骤(1),直接将NaY分子筛用于步骤(2)中,其余步骤同实施例1,得到CaO-MgO-V2O5/NaY分子筛催化剂。
将CaO-MgO-V2O5/NaY分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,步骤同实施例1。得到甲基丙烯酸二甲基氨基乙酯产品142.33g,收率为84.2%,纯度93.0%。该催化剂使用1个月时,其催化合成得到的甲基丙烯酸二甲基氨基乙酯的收率为78.9%。
对比例3
在分子筛催化剂的制备过程步骤(2)中,不加入镁和钙,将相应的镁和钙全部替换为钠,其余步骤同实施例1。将得到的分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,步骤同实施例1;反应无法进行,无法得到甲基丙烯酸二甲基氨基乙酯产品。
对比例4
在分子筛催化剂的制备过程步骤(2)中,加入镁,不加入钙,将相应的钙全部替换为镁,其余步骤同实施例1。将得到的分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,步骤同实施例1;反应产率较低,仅为81.4%,纯度93.5%。
对比例5
在分子筛催化剂的制备过程步骤(2)中,加入钙,不加入镁,将相应的镁全部替换为钙,其余步骤同实施例1。将得到的分子筛催化剂用于以甲基丙烯酸甲酯和二甲基氨基乙醇为原料合成甲基丙烯酸二甲基氨基乙酯的过程中,步骤同实施例1;反应产率也不高,仅为82.7%,纯度95.8%。
经过6个月的运行,使用实施例1-3催化剂进行生产的收率数据如下:
实施例1,初始98%,1个月97.8%,2个月97.5%,3个月97.3%,4个月96.9%,5个月96.8%,6个月96.5%。
实施例2,初始98.5%,1个月98.3%,2个月98.1%,3个月97.7%,4个月97.4%,5个月97.1%,6个月96.8%。
实施例3,初始98.7%,1个月98.6%,2个月98.3%,3个月97.8%,4个月97.5%,5个月97.4%,6个月97.1%。
由实施例1-3和对比例1-5的收率数据可知,实施例1-3的催化剂,使用6个月后,效果依然维持在一个令人满意的水平。而对比例1-2的催化剂使用1个月时的收率下降很快,不再进行后续的评价实验。对比例3-5初始收率均低于对比例1-2的初始收率,也没有必要继续评价实验。
本发明Na2O-CaO-MgO-V2O5/LaY分子筛催化剂中,Na2O-CaO-MgO提供碱性位,采用Na、Ca、Mg三者的组合,使得分子筛催化剂碱性适中,有利于V的分布。
因此,本发明的三个步骤缺一不可,缺少步骤以及不按本发明步骤进行生产均不能获得显著的进步。
Claims (10)
1.一种用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂,其特征在于该分子筛催化剂为Na2O-CaO-MgO-V2O5/LaY,其中Na2O:CaO:MgO:V2O5的质量比为1:1.9-2.1:2.0-2.2:1,LaY中La含量为7-10wt.%;Na2O-CaO-MgO-V2O5/LaY中Na2O-CaO-MgO-V2O5的总质量为LaY质量的25-35%。
2.一种权利要求1所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的制备方法,其特征在于包括以下步骤:
(1)将NaY分子筛制成浆液,加入硝酸镧溶液进行离子交换,得到混合浆液;
(2)向步骤(1)得到的混合浆液中加入表面活性剂,同时加入硝酸镁与硝酸钙混合水溶液、氨水进行共沉淀,经老化、烘干、焙烧得到Na2O-CaO-MgO/LaY分子筛;
(3)将步骤(2)得到的Na2O-CaO-MgO/LaY分子筛于偏钒酸铵溶液中浸渍,再经烘干、焙烧得到Na2O-CaO-MgO-V2O5/LaY分子筛催化剂。
3.根据权利要求2所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的制备方法,其特征在于:步骤(1)为:将NaY分子筛制成浆液,超声30-35min后升温至70-80℃,再加入25-35wt.%的硝酸镧溶液进行离子交换2-4h,得到混合浆液;所述的硝酸镧溶液中硝酸镧与NaY分子筛的质量比0.07-0.1:1。
4.根据权利要求2所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的制备方法,其特征在于:NaY分子筛与表面活性剂、硝酸镁与硝酸钙混合水溶液中溶质、氨水中溶质的质量比为100:2:170-175:35-40;所述的硝酸镁与硝酸钙混合水溶液的浓度为20-30wt.%,其中硝酸镁与硝酸钙的质量比为1.26:1;所述的氨水的浓度为10-15wt.%。
5.根据权利要求2所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的制备方法,其特征在于:步骤(2)中,所述的表面活性剂为羟甲基纤维素、羟乙基纤维素、聚丙烯酰胺或聚乙二醇600;共沉淀时间为60-90min,共沉淀温度为70-80℃;老化时间为3-5h;焙烧温度为500-550℃。
6.根据权利要求2所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的制备方法,其特征在于:步骤(3)中,50-60℃下,将步骤(2)得到的Na2O-CaO-MgO/LaY分子筛于偏钒酸铵溶液中饱和浸渍3-3.5h;焙烧温度为450-500℃。
7.一种权利要求1所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的应用,其特征在于:以甲基丙烯酸甲酯和二甲基氨基乙醇为原料经混合后连续化进入反应精馏塔,反应精馏塔中装填Na2O-CaO-MgO-V2O5/LaY分子筛催化剂,在反应精馏塔中进行连续化催化酯交换反应,塔顶连续化采出甲醇-甲基丙烯酸甲酯共沸物,塔釜连续化采出粗产品,经精馏得到甲基丙烯酸二甲基氨基乙酯产品。
8.根据权利要求7所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的应用,其特征在于:甲基丙烯酸甲酯与二甲基氨基乙醇的摩尔比为2-4:1。
9.根据权利要求7所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的应用,其特征在于:连续化催化酯交换反应的温度为100-120℃,压力为0.3-0.8MPa。
10.根据权利要求7所述的用于合成甲基丙烯酸二甲基氨基乙酯的分子筛催化剂的应用,其特征在于:反应精馏塔塔顶的摩尔回流比为8-12;连续化催化酯交换反应的质量空速范围为0.8-1.2g/(g·h)。
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