完全无氯铜基催化剂制备与催化甲醇氧化羰基化的研究
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摘要
被誉为有机合成“新基石”的碳酸二甲酯(DMC)是一种重要的有机合成中间体,可以代替剧毒或致癌的光气、硫酸二甲酯等,用作甲基化、羰基化以及甲氧基化的化工生产。DMC也是性质优良的溶剂和汽油添加剂。在众多DMC的合成工艺中,甲醇气相氧化羰基化法由于其过程简单、环境友好、成本低而引起人们的极大关注。
金属氯化物负载催化剂具有较好的催化活性,但由于Cl离子流失使催化剂寿命短、易失活,且腐蚀设备。由CuCl和酸性分子筛载体固相离子交换制备的CuI/分子筛催化剂,具有氯含量低、稳定性较好的特点,表面Cu_2(OH)_3Cl物种的形成与催化活性密切相关,但仍存在氯流失的问题。本文首先采用CuCl_2替代CuCl与HY型分子筛进行固体离子交换制备了CuI/Y催化剂,研究了负载Cu_2(OH)_3Cl催化剂的催化性能和稳定性,并通过Cu~(2+)溶液与NaY分子筛离子交换和Cu_2(OH)_3NO_3/活性炭(AC)热处理,实现了具有较好催化活性的完全无氯负载型Cu基催化剂的制备,并通过多种表征和分析手段,研究了催化剂结构、活性中心及催化活性之间的关系,获得的主要研究结论如下:
(1)在惰性气氛下,CuCl_2·2H_2O在低于200℃，下加热,脱除结晶水;在300℃到550℃之间加热,CuCl_2分解生成CuCl和Cl_2;温度高于550℃,CuCl快速升华。证明了CuCl_2热分解为CuCl的温度和固体离子交换温度一致。
(2)研究了CuCl_2·2H_2O能够取代CuCl进行固体离子交换制备CuI/Y催化剂。在惰性气氛下,加热处理CuCl_2·2H_2O和HY分子筛混合样品,脱除结晶水的CuCl_2在300℃到550℃之间分解生成CuCl,CuCl进一步与HY发生固相离子交换反应生成Cu/Y分子筛催化剂;当加热温度高于550℃时,催化剂表面的CuCl升华。
(3)表征分析表明,以CuCl_2·2H_2O和HY分子筛加热处理获得的Cu/Y催化剂中,活性金属Cu在分子筛表面以CuCl或CuCl_2形式存在,而在分子筛笼内以交换的Cu+和少量吸附的CuCl形式存在。比CuCl和HY制备的催化剂具有更低的Cu和Cl含量,却表现出较高的催化活性。当加热温度为650oC时制备的CuI/Y催化剂具有较高的气相甲醇氧化羰基化的催化活性,DMC的时空收率(STY)为110mg/(g·h),选择性(SDMC)为72.56%。
(4)研究表明,负载Cu_2(OH)_3Cl的催化剂比负载CuCl_2的催化剂具有更好的催化活性和稳定性,且活性炭载体最好。Cu含量为18.7%的Cu_2(OH)_3Cl/AC催化剂, DMC的STY, SDMC和CMeOH分别达到139.1mg/(g·h),67.3%和6.93%。
(5)在甲醇氧化羰基化反应过程中,Cu_2(OH)_3Cl/AC催化剂表面的Cu_2(OH)_3Cl晶粒逐渐团聚变大,并且部分转化为CuCl_2和CuO而导致其催化活性降低,而且原催化剂中唯一的CuⅡ物种部分转化为CuI物种。
(6)采用无氯Cu~(2+)盐进行溶液离子交换,制备的完全无氯CuNaY催化剂的催化活性较低。Cu~(2+)盐的阴离子影响到溶液的pH值,使Cu~(2+)的存在形式不同,导致Cu~(2+)的交换量不同,催化活性不同。滴加氨水调节Cu~(2+)盐水溶液的pH值为12后,Cu~(2+)形成铜氨络合离子,所制备的CuNaY催化剂的催化活性和DMC选择性明显升高,且趋于一致。
(7)采用Cu(NO_3)2溶液离子交换制备催化剂时,随着NH_3量的增加,形成的铜氨溶液pH值升高,CuNaY催化剂中Cu含量升高,催化活性也升高。当pH值由3增加到10时,催化活性增加比较明显,当pH大于10时,Cu~(2+)交换量变化较小,活性增加趋于缓和。
(8)在惰性气氛下,加热处理Cu_2(NO_3)(OH)3/AC前驱体,可获得完全无氯负载CuO/AC、Cu_2O/AC和Cu/AC催化剂。在200℃下加热,活性组分主要为CuO。随着加热温度升高,催化剂中CuO逐步转化为Cu_2O。在300℃~400℃下加热制备的催化剂为Cu_2O/AC,当在450℃以上加热时获得Cu0/AC催化剂。
(9)加热处理Cu_2(NO_3)(OH)3/AC制备的催化剂的甲醇氧化羰基化催化活性顺序为:CuO/AC (10)添加Zn元素可改善Cu/AC催化剂的稳定性。Cu/Zn摩尔比为2,制备温度为400℃时,所得的Cu-Zn/AC催化剂催化活性最高。在24h的反应过程中DMC的STY与选择性分别达到122.24 mg/(g·h)和73.46%。
As an environment benign green-chemical, dimethyl carbonate (DMC) is regarded as“new building block”in organic synthesis. It can served as green and safe substitute for phosgene and dimethyl sulfate, which are highly toxic and corrosive used in commercial chemical processes of methylatiion and carbonylation. In addition, DMC is also good solvent and additive in gasoline. In the all routs of DMC synthsis, vapor phase oxidative carbonylation of methanol to DMC has been considered as the most promising way because of its simple process, friendly environment and low cost.
In the process of oxidative carbonylation of methanol in vapor phase, metal chloride supported catalysts have good activity but suffer from the quick deactivation and equipment corrison due to the loss of chlorine during the reaction running. Prepared by solid-state ion-exchange reaction of CuCl and acidic zeolite, the CuI/zeolite with low chlorine exhibited good activity and stability,but still suffer from the loss of chlorine. In this thesis, CuCl_2·2H_2O was used as substitute of CuCl to produce CuI/Y catalyst by solid-state ion-exchange reaction, and the preparation process and morphological structure of the CuI/Y catalyst were characterized. The supported Cu_2(OH)_3Cl catalyst were also studied. By aqueous ion-exchange reaction of Cu~(2+) and NaY zeolite or heat treatment of Cu_2(OH)_3NO_3/AC precursor, the chlorine-free copper catalysts were made and studied. The micro-structure, active species of catalysts were analyzed by CO-TPD, XRD, TG-DTG, XPS, SEM and EA technics. The obtained main conclusions are listed as following.
(1) Under inert atmosphere, CuCl_2·2H_2O lost its crystal water below 200oC, and decomposed into CuCl and Cl_2 gas between 300°C and 550°C, then the formed CuCl sublimated above 550°C. The temperature of CuCl_2 decomposition to CuCl is in the range of of solid-state ion-exchange temperature between CuCl and HY zeolite.
(2) CuCl_2·2H_2O can substitute CuCl to prepared CuI/Y catalyst by solid-state ion-exchange reaction. Under inert atmosphere, the CuCl_2 by dehydration of CuCl_2·2H_2O decomposed into CuCl and Cl_2 from 300℃to 550℃, the produced CuCl ion-exchanged with HY zeolite to form Cu/Y catalyst; the extra CuCl in the surface of catalyst sublimed above 550℃.
(3) In the Cu/Y catalyst prepared by heat treatment of CuCl_2·2H_2O and HY zeolite, the Cu existed in the form of CuCl or CuCl_2 in the zeolite surface, while ion- exchanged Cu+ and little adsorbed CuCl in the zeolite cages. Comparing to the catalysts from CuCl and HY zeolite, the catalysts from CuCl_2·2H_2O and HY zeolite have lower Cu and Cl amount, but higher catalytic activity in the oxidative carbonylation of methanol in vapour phase, the space-time yield of DMC was 110mg(g·h), selectivity of DMC was 72.56%.
(4) The catalytic activity and stability of Cu_2(OH)_3Cl supported catalysts were higher than that of CuCl_2 supported catalyst, activated carbon was the best support. The methanol conversion, selectivity and space time yield of DMC on the Cu_2(OH)_3Cl/AC of 18.71% Cu were 6.93 %, 67.3 % and 139.13 mg/(g·h) respectivly.
(5) The dispersion property of Cu_2(OH)_3Cl in Cu_2(OH)_3Cl/AC catalyst was getting worse and the Cu_2(OH)_3Cl was transformed to CuCl_2 and CuO during the reaction, resulting in the decrease of catalytic activity. The unique CuⅡ species in the fresh catalyst transferred into CuI species partially during the reaction.
(6) The chlorine-free CuNaY catalysts prepared by ion-exchange reaction of NaY zeolite and Cu~(2+) aqueous solution were poor in catalytic activity. When the pH value of Cu~(2+) aqueous solution was adjusted to 12 by adding of ammonia, the copper ammonia complex was formed, and the catalytic activity and selectivity of DMC increased greatly.
(7) With the adding of ammonia, the pH value of copper nitrate solution increased, the ion-exchanged CuⅡand catalytic activity of the produced CuNaY catalyst increased consequently. The increase of catalytic activity was obvious when the pH value was between 3 to 10, and unconspicuous when the pH value was above 10.
(8) Under inert atmosphere, the chlorine free CuO/AC, Cu_2O/AC or Cu/AC catalyst can be obtained by heat treatment of Cu_2(NO_3)(OH)3/AC precursor sample. When heated under 200°C, the main product on AC support was CuO. With heating temperature rising, the CuO turned to Cu_2O gradually. The Cu_2O/AC was obtained under 300°C to 400°C, and Cu0/AC was under 450°C.
(9) In oxidative carbonylation of methanol in vapor phase, the catalytic activity of the catalyst by heat treatment of Cu_2(NO_3)(OH)3 /AC increased in the sequences of CuO/AC (10) The stability of Cu/AC catalysts can be improved by adding of Zn element. When the heating temperature was 400°C, the Cu-Zn/AC catalyst with Cu/Zn molar ratio of 2 exhibited the best catalytic activity. The STY and selectivity of DMC were 122.24 mg/(g·h) and 73.46% in the 24h reaction.
金属氯化物负载催化剂具有较好的催化活性,但由于Cl离子流失使催化剂寿命短、易失活,且腐蚀设备。由CuCl和酸性分子筛载体固相离子交换制备的CuI/分子筛催化剂,具有氯含量低、稳定性较好的特点,表面Cu_2(OH)_3Cl物种的形成与催化活性密切相关,但仍存在氯流失的问题。本文首先采用CuCl_2替代CuCl与HY型分子筛进行固体离子交换制备了CuI/Y催化剂,研究了负载Cu_2(OH)_3Cl催化剂的催化性能和稳定性,并通过Cu~(2+)溶液与NaY分子筛离子交换和Cu_2(OH)_3NO_3/活性炭(AC)热处理,实现了具有较好催化活性的完全无氯负载型Cu基催化剂的制备,并通过多种表征和分析手段,研究了催化剂结构、活性中心及催化活性之间的关系,获得的主要研究结论如下:
(1)在惰性气氛下,CuCl_2·2H_2O在低于200℃，下加热,脱除结晶水;在300℃到550℃之间加热,CuCl_2分解生成CuCl和Cl_2;温度高于550℃,CuCl快速升华。证明了CuCl_2热分解为CuCl的温度和固体离子交换温度一致。
(2)研究了CuCl_2·2H_2O能够取代CuCl进行固体离子交换制备CuI/Y催化剂。在惰性气氛下,加热处理CuCl_2·2H_2O和HY分子筛混合样品,脱除结晶水的CuCl_2在300℃到550℃之间分解生成CuCl,CuCl进一步与HY发生固相离子交换反应生成Cu/Y分子筛催化剂;当加热温度高于550℃时,催化剂表面的CuCl升华。
(3)表征分析表明,以CuCl_2·2H_2O和HY分子筛加热处理获得的Cu/Y催化剂中,活性金属Cu在分子筛表面以CuCl或CuCl_2形式存在,而在分子筛笼内以交换的Cu+和少量吸附的CuCl形式存在。比CuCl和HY制备的催化剂具有更低的Cu和Cl含量,却表现出较高的催化活性。当加热温度为650oC时制备的CuI/Y催化剂具有较高的气相甲醇氧化羰基化的催化活性,DMC的时空收率(STY)为110mg/(g·h),选择性(SDMC)为72.56%。
(4)研究表明,负载Cu_2(OH)_3Cl的催化剂比负载CuCl_2的催化剂具有更好的催化活性和稳定性,且活性炭载体最好。Cu含量为18.7%的Cu_2(OH)_3Cl/AC催化剂, DMC的STY, SDMC和CMeOH分别达到139.1mg/(g·h),67.3%和6.93%。
(5)在甲醇氧化羰基化反应过程中,Cu_2(OH)_3Cl/AC催化剂表面的Cu_2(OH)_3Cl晶粒逐渐团聚变大,并且部分转化为CuCl_2和CuO而导致其催化活性降低,而且原催化剂中唯一的CuⅡ物种部分转化为CuI物种。
(6)采用无氯Cu~(2+)盐进行溶液离子交换,制备的完全无氯CuNaY催化剂的催化活性较低。Cu~(2+)盐的阴离子影响到溶液的pH值,使Cu~(2+)的存在形式不同,导致Cu~(2+)的交换量不同,催化活性不同。滴加氨水调节Cu~(2+)盐水溶液的pH值为12后,Cu~(2+)形成铜氨络合离子,所制备的CuNaY催化剂的催化活性和DMC选择性明显升高,且趋于一致。
(7)采用Cu(NO_3)2溶液离子交换制备催化剂时,随着NH_3量的增加,形成的铜氨溶液pH值升高,CuNaY催化剂中Cu含量升高,催化活性也升高。当pH值由3增加到10时,催化活性增加比较明显,当pH大于10时,Cu~(2+)交换量变化较小,活性增加趋于缓和。
(8)在惰性气氛下,加热处理Cu_2(NO_3)(OH)3/AC前驱体,可获得完全无氯负载CuO/AC、Cu_2O/AC和Cu/AC催化剂。在200℃下加热,活性组分主要为CuO。随着加热温度升高,催化剂中CuO逐步转化为Cu_2O。在300℃~400℃下加热制备的催化剂为Cu_2O/AC,当在450℃以上加热时获得Cu0/AC催化剂。
(9)加热处理Cu_2(NO_3)(OH)3/AC制备的催化剂的甲醇氧化羰基化催化活性顺序为:CuO/AC
As an environment benign green-chemical, dimethyl carbonate (DMC) is regarded as“new building block”in organic synthesis. It can served as green and safe substitute for phosgene and dimethyl sulfate, which are highly toxic and corrosive used in commercial chemical processes of methylatiion and carbonylation. In addition, DMC is also good solvent and additive in gasoline. In the all routs of DMC synthsis, vapor phase oxidative carbonylation of methanol to DMC has been considered as the most promising way because of its simple process, friendly environment and low cost.
In the process of oxidative carbonylation of methanol in vapor phase, metal chloride supported catalysts have good activity but suffer from the quick deactivation and equipment corrison due to the loss of chlorine during the reaction running. Prepared by solid-state ion-exchange reaction of CuCl and acidic zeolite, the CuI/zeolite with low chlorine exhibited good activity and stability,but still suffer from the loss of chlorine. In this thesis, CuCl_2·2H_2O was used as substitute of CuCl to produce CuI/Y catalyst by solid-state ion-exchange reaction, and the preparation process and morphological structure of the CuI/Y catalyst were characterized. The supported Cu_2(OH)_3Cl catalyst were also studied. By aqueous ion-exchange reaction of Cu~(2+) and NaY zeolite or heat treatment of Cu_2(OH)_3NO_3/AC precursor, the chlorine-free copper catalysts were made and studied. The micro-structure, active species of catalysts were analyzed by CO-TPD, XRD, TG-DTG, XPS, SEM and EA technics. The obtained main conclusions are listed as following.
(1) Under inert atmosphere, CuCl_2·2H_2O lost its crystal water below 200oC, and decomposed into CuCl and Cl_2 gas between 300°C and 550°C, then the formed CuCl sublimated above 550°C. The temperature of CuCl_2 decomposition to CuCl is in the range of of solid-state ion-exchange temperature between CuCl and HY zeolite.
(2) CuCl_2·2H_2O can substitute CuCl to prepared CuI/Y catalyst by solid-state ion-exchange reaction. Under inert atmosphere, the CuCl_2 by dehydration of CuCl_2·2H_2O decomposed into CuCl and Cl_2 from 300℃to 550℃, the produced CuCl ion-exchanged with HY zeolite to form Cu/Y catalyst; the extra CuCl in the surface of catalyst sublimed above 550℃.
(3) In the Cu/Y catalyst prepared by heat treatment of CuCl_2·2H_2O and HY zeolite, the Cu existed in the form of CuCl or CuCl_2 in the zeolite surface, while ion- exchanged Cu+ and little adsorbed CuCl in the zeolite cages. Comparing to the catalysts from CuCl and HY zeolite, the catalysts from CuCl_2·2H_2O and HY zeolite have lower Cu and Cl amount, but higher catalytic activity in the oxidative carbonylation of methanol in vapour phase, the space-time yield of DMC was 110mg(g·h), selectivity of DMC was 72.56%.
(4) The catalytic activity and stability of Cu_2(OH)_3Cl supported catalysts were higher than that of CuCl_2 supported catalyst, activated carbon was the best support. The methanol conversion, selectivity and space time yield of DMC on the Cu_2(OH)_3Cl/AC of 18.71% Cu were 6.93 %, 67.3 % and 139.13 mg/(g·h) respectivly.
(5) The dispersion property of Cu_2(OH)_3Cl in Cu_2(OH)_3Cl/AC catalyst was getting worse and the Cu_2(OH)_3Cl was transformed to CuCl_2 and CuO during the reaction, resulting in the decrease of catalytic activity. The unique CuⅡ species in the fresh catalyst transferred into CuI species partially during the reaction.
(6) The chlorine-free CuNaY catalysts prepared by ion-exchange reaction of NaY zeolite and Cu~(2+) aqueous solution were poor in catalytic activity. When the pH value of Cu~(2+) aqueous solution was adjusted to 12 by adding of ammonia, the copper ammonia complex was formed, and the catalytic activity and selectivity of DMC increased greatly.
(7) With the adding of ammonia, the pH value of copper nitrate solution increased, the ion-exchanged CuⅡand catalytic activity of the produced CuNaY catalyst increased consequently. The increase of catalytic activity was obvious when the pH value was between 3 to 10, and unconspicuous when the pH value was above 10.
(8) Under inert atmosphere, the chlorine free CuO/AC, Cu_2O/AC or Cu/AC catalyst can be obtained by heat treatment of Cu_2(NO_3)(OH)3/AC precursor sample. When heated under 200°C, the main product on AC support was CuO. With heating temperature rising, the CuO turned to Cu_2O gradually. The Cu_2O/AC was obtained under 300°C to 400°C, and Cu0/AC was under 450°C.
(9) In oxidative carbonylation of methanol in vapor phase, the catalytic activity of the catalyst by heat treatment of Cu_2(NO_3)(OH)3 /AC increased in the sequences of CuO/AC
引文
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