CN113634278B - 催化2,5-二甲基呋喃和乙醇制取对二甲苯的催化剂的制备方法 - Google Patents
催化2,5-二甲基呋喃和乙醇制取对二甲苯的催化剂的制备方法 Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
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- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 33
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
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- 239000010457 zeolite Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
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- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000005580 one pot reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 10
- 238000006352 cycloaddition reaction Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/76—Iron group metals or copper
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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Abstract
本发明涉及催化剂制备技术，旨在提供一种催化2,5‑二甲基呋喃和乙醇制取对二甲苯的催化剂的制备方法。该方法包括：将金属前驱体溶于溶剂中，加入配体与金属前驱体进行络合反应，得到反应液；将沸石粉末加入反应液中，搅拌得到完成金属阳离子交换的沸石；进行抽滤、水洗和干燥，焙烧得到催化剂产品。本发明的催化剂可以实现一锅催化2,5‑二甲基呋喃和乙醇直接反应制备对二甲苯，无需分段操作，过程简单；催化剂的寿命较长，即使在反应过程中由于积碳而导致活性下降，也可以通过简单的焙烧程序再生催化剂；原料价格较低、制备过程简单。
Description
技术领域
本发明属于催化剂制备技术，特别涉及到一种催化2,5-二甲基呋喃和乙醇制对二甲苯的催化剂的制备方法。
背景技术
对二甲苯是化工行业常说的“三苯”之一，主要用于生产聚对苯二甲酸乙二醇酯(PET)的原料对苯二甲酸。由于PET具有耐热、机械性能好、可塑性强等优点，是人类生产生活所必需的大宗化学品，因此开发可持续的碳中和的路线生产对二甲苯就显得尤为重要。
已有研究人员提出采用2,5-二甲基呋喃与乙烯发生环加成反应制备对二甲苯。纤维素是植物经过光合作用产生的原料，可以通过催化转化生成5-羟甲基糠醛、乙醇等产品。通过乙醇脱水制备乙烯，将其作为环加成反应制备对二甲苯的原料。在此基础上，纤维素基原料——乙醇——乙烯——对二甲苯的生产路径是一条绿色的碳中和的路线。然而在这个过程中，乙烯需要通过乙醇脱水获得，额外产生了生产成本和分离流程。而现有技术中的乙醇脱水与乙烯环加成反应的条件不匹配，如要以乙醇为起点制备对二甲苯，就必须分为两个反应阶段，两个阶段分别使用单独的催化剂；导致存在整个生产流程多、工艺条件复杂、综合成本高等问题。
一锅法生产是现代化工生产中的一种择优方案，因为可以最大程度简化生产流程，节约成本。但基于上述原因，要直接催化乙醇与2,5-二甲基呋喃以制备对二甲苯，就需要开发新的催化剂。
发明内容
本发明要解决的技术问题是，克服现有技术中的不足，提供一种催化2,5-二甲基呋喃和乙醇制取对二甲苯的催化剂的制备方法。
为解决技术问题，本发明的解决方案是：
提供一种催化2,5-二甲基呋喃和乙醇制取对二甲苯的催化剂的制备方法，包括以下步骤：
(1)将金属前驱体溶于溶剂中，得到前驱体溶液；加入配体与金属前驱体进行络合反应，得到反应液；
(2)将沸石粉末加入步骤(1)的反应液中，在25～100℃下搅拌1～24小时，得到完成金属阳离子交换的沸石；
(3)对步骤(2)中完成金属阳离子交换的沸石进行抽滤、水洗和干燥，然后在200～500℃焙烧0.1～10小时，得到用于催化2,5-二甲基呋喃和乙醇制备多取代芳烃的催化剂；在该催化剂中，金属阳离子的质量分数为0.1～10％。
作为本发明的优选方案，所述金属前驱体中的金属元素是铁、钴、镍、铜、锌、铝、钛、铟、锡、镧、铈、铋中的任意一种，其前驱体为硝酸盐、氯化物、醋酸盐、乙酰丙酮盐中的任意一种。
作为本发明的优选方案，所用溶剂是水、甲醇、乙醇、丙酮、乙酰丙酮、氮,氮-二甲基甲酰胺、戊内酯中的任意一种。
作为本发明的优选方案，所用配体是氨水、乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、乙二胺四乙酸二钠中的任意一种，配体与金属前驱体中金属元素的摩尔比为0.1～10。
作为本发明的优选方案，所用沸石为*BEA、MOR、MFI、FAU中的任意一种。
作为本发明的优选方案，所述前驱体溶液的浓度为0.001～5mol/L。
作为本发明的优选方案，所述反应液与沸石粉末的体积质量比例为1～100mL/g。
本发明制备得到的催化剂可以应用于催化2,5-二甲基呋喃和乙醇制备多取代芳烃的反应中。
发明原理描述：
沸石是一种具有丰富均匀微孔的硅铝酸盐晶体。因其可以调变的酸强度和酸量以及筛分不同尺寸分子的能力而具有非常优异的性能。目前分子筛被广泛应用于石油化工中的催化裂化，异构化等反应中。沸石的催化性能与其酸性有很大关系，而沸石的酸性可以通过阳离子交换的方式调节。例如将铜离子引入CHA分子筛上后便会大大增加其酸量，在催化乙醇脱水反应中有非常优异的表现。
沸石本身可以催化2,5-二甲基呋喃和乙烯发生环加成反应。本发明通过阳离子交换的方式调控沸石酸量和酸强度，使其可以将乙醇脱水与环加成反应耦合，实现一锅催化2,5-二甲基呋喃和乙醇直接反应制备对二甲苯。
区别于现有生产路线中不同反应使用不同催化剂，或者混合使用多种催化剂的做法，本发明提供了全新的催化剂制备思路：在沸石中控制好阳离子的落位，以特定位置引入额外的阳离子，实现不同酸位点的协同催化。
其微观层面的原理：为实现一锅催化2,5-二甲基呋喃和乙醇直接反应制备对二甲苯，需要将乙醇脱水制乙烯与2,5-二甲基呋喃和乙烯环加成两个反应耦合起来。前者需要路易斯酸位点，后者需要沸石本身的酸位点，两种酸位点在空间上应尽可能接近才能实现协同作用。为了构筑这样一个催化剂，本发明选择铁、钴、镍、铜、锌、铝、钛、铟、锡、镧、铈、铋等金属的阳离子与配体络合后选择性地锚定到沸石原本的酸位点附近，焙烧后可以在沸石中引入丰富的路易斯酸位点；选择BEA、MOR、MFI、FAU等可以高效催化环加成反应的沸石，不但保证环加成反应可以顺利进行，还可以保证金属阳离子在其中均匀分散。这样在沸石晶体中同时具有两种酸位点，可以高效地催化2,5-二甲基呋喃和乙醇直接反应制备对二甲苯。并且沸石晶体又赋予了催化剂较高的稳定性，使得催化剂同时具有高活性和高稳定性。
与现有技术相比，本发明的有益效果在于：
1、本发明方法合成的催化剂可以实现一锅催化2,5-二甲基呋喃和乙醇直接反应制备对二甲苯，而其它路线则需要分阶段使用两种以上催化剂，不同阶段反应条件不匹配，需分段操作，过程复杂；
2、本发明的催化剂的寿命较长，沸石赋予了催化剂较高的稳定性，即使在反应过程中由于积碳而导致活性下降，也可以通过简单的焙烧程序再生催化剂；
3、本发明的催化剂制备所需的原料价格较低、制备过程简单。
具体实施方式
以下通过具体实施例对有关内容进行详细表述。
本发明所述催化2,5-二甲基呋喃和乙醇制备多取代芳烃的催化剂，其制备方法包括以下步骤：
(1)将金属前驱体溶于溶剂中，得到浓度为0.001～5mol/L的前驱体溶液；加入配体与金属前驱体进行络合反应，得到反应液；所述金属前驱体中的金属元素是铁、钴、镍、铜、锌、铝、钛、铟、锡、镧、铈、铋中的任意一种，其前驱体为硝酸盐、氯化物、醋酸盐、乙酰丙酮盐中的任意一种。所用溶剂是水、甲醇、乙醇、丙酮、乙酰丙酮、氮，氮-二甲基甲酰胺、戊内酯中的任意一种。所用配体是氨水、乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、乙二胺四乙酸二钠中的任意一种，配体与金属前驱体中金属元素的摩尔比为0.1～10。
(2)将沸石粉末加入步骤(1)的反应液中，反应液与沸石粉末的体积质量比例为1～100mL/g；在25～100℃下搅拌1～24小时，得到完成金属阳离子交换的沸石；所用沸石为*BEA、MOR、MFI、FAU中的任意一种。
(3)对步骤(2)中完成金属阳离子交换的沸石进行抽滤、水洗和干燥，然后在200～500℃焙烧0.1～10小时，得到催化剂；在该催化剂中，金属阳离子的质量分数为0.1～10％。
本发明的催化剂可以用于催化2,5-二甲基呋喃和乙醇制备对二甲苯，并通过下述示例方法对本发明的催化剂效果进行验证：
通过高压充气反应釜评价催化剂的性能：将催化剂、反应物和溶剂放置于反应釜内；催化剂用量为600mg，2,5-二甲基呋喃5mmol，乙醇7.5mmol，30毫升正癸烷作为溶剂。将反应釜密封后，用氮气排气五次，然后充入2MPa氮气。开启机械搅拌，将反应温度升至300℃，保持10小时，反应后将反应釜置于冰水浴中降温。
采用气相色谱分析反应液的产物组成(见表1中乙醇转化率、2,5-二甲基呋喃转化率、对二甲苯产率的数据)。
本发明通过16个实施例制备得到催化剂，并分别用于多取代芳烃的制备中。各实施例中的试验数据见下表1。
表1.实施例数据表
从表1中的数据可以看出，本发明通过简单的方法修饰了沸石催化剂，使其可以实现一锅催化2,5-二甲基呋喃和乙醇直接反应制备对二甲苯，反应路径更短，避免了过程复杂的分段反应带来的繁琐操作。
虽然本发明只针对催化2,5-二甲基呋喃和乙醇直接反应制备对二甲苯提供了实施例数据，但基于相类似的反应原理，本领域技术人员也可以想到，针对2,5-二甲基呋喃具有相近似化学结构和性能的其它呋喃衍生物，也可以使用本发明提出的催化剂进行反应以制取其它多取代芳烃。
最后，需要注意的是，以上列举的仅是本发明的具体实施例。显然，本发明不限于以上实施例，还可以有很多变形。本领域的普通技术人员能从本发明公开的内容中直接导出或联想到的所有变形，均应认为是本发明的保护范围。
Claims (3)
1.一种催化2,5-二甲基呋喃和乙醇制取对二甲苯的方法，其特征在于，其催化剂的制备包括以下步骤：
（1）将金属前驱体溶于溶剂中，得到前驱体溶液；加入配体与金属前驱体进行络合反应，得到反应液；
所述金属前驱体中的金属元素是铁、钴、镍、铜、锌、铝、钛、铟、锡、镧、铈、铋中的任意一种，其前驱体为硝酸盐、氯化物、醋酸盐、乙酰丙酮盐中的任意一种；所用溶剂是水、甲醇、乙醇、丙酮、乙酰丙酮、氮,氮-二甲基甲酰胺、戊内酯中的任意一种；所用配体是氨水、乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、乙二胺四乙酸二钠中的任意一种，配体与金属前驱体中金属元素的摩尔比为0.1~10；
（2）将沸石粉末加入步骤（1）的反应液中，在25～100℃下搅拌1～24小时，得到完成金属阳离子交换的沸石；
所用沸石为*BEA、MOR、MFI、FAU中的任意一种；
（3）对步骤（2）中完成金属阳离子交换的沸石进行抽滤、水洗和干燥，然后在200～500℃焙烧0.1～10小时，得到催化剂；在该催化剂中，金属阳离子的质量分数为0.1~10%。
2.根据权利要求1所述的方法，其特征在于，所述前驱体溶液的浓度为0.001～5mol/L。
3.根据权利要求1所述的方法，其特征在于，所述反应液与沸石粉末的体积质量比例为1～100mL/g。
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