CN106365936B - 液相醇脱氢的列管式反应器及液相醇脱氢的方法 - Google Patents

液相醇脱氢的列管式反应器及液相醇脱氢的方法 Download PDF

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CN106365936B
CN106365936B CN201610733149.XA CN201610733149A CN106365936B CN 106365936 B CN106365936 B CN 106365936B CN 201610733149 A CN201610733149 A CN 201610733149A CN 106365936 B CN106365936 B CN 106365936B
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dehydrogenation
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CN106365936A (zh
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郑辉东
孔委
张健文
林毅
严佐毅
王莹淑
吴丹
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Fuzhou University
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Abstract

本发明涉及一种液相醇脱氢的列管式反应器及液相醇脱氢的方法，醇脱氢反应大多为吸热反应，反应温度较高，平衡转化率偏低。本发明采用列管式的氢气选择透过性的膜组件反应器，在膜两侧分别进行醇液相脱氢反应和氢气气相氧化反应：即脱氢反应产物氢气及时渗透出反应体系，不仅提高了反应速率，也提高了该反应的平衡转化率，而渗透侧通过控制氧化反应的速率可为醇脱氢提供适宜的热量，从而达到原位供热的目的。

Description

液相醇脱氢的列管式反应器及液相醇脱氢的方法
技术领域：
本发明涉及一种热耦合膜反应器，主要应用于醇的液相脱氢过程，利用膜的选择渗透性，可实现在膜的一侧进行吸热的脱氢反应，而另一侧进行放热的氧化反应，达到实现原位供热、提高脱氢反应的转化率以及选择性和节能的目的。
背景技术：
由醇制备羰基化合物是有机化学最基本、最重要的反应之一，在化工生产中有着广泛应用。目前，醇制备羰基化合物主要有两种方法：一种是催化氧化法，利用氧化剂和催化剂共同作用制备羰基化合物，该方法副反应较多，且容易产生有毒和危害性的废弃物；另一种是催化脱氢法，即在催化剂作用下直接脱除氢气，反应方程式如式（1）所示，醇脱氢相对容易实现，其反应温度较其它脱氢过程较低，因此副产物少，选择性高，但是工业上传统的脱氢工艺大都在气相中进行，反应温度较高，热量消耗大，平衡转化率受反应平衡和温度制约因而不高。因此，使用液相脱氢的方法可以避免以上缺陷，反应条件相对温和，目标产物的选择性高，是一种优选的方法。
（1）
催化脱氢过程具体的实施可分为直接脱氢路径和转移脱氢路径，由于一般的直接脱氢路径有一个最大的不足即平衡转化率偏低，因为反应产物醛/酮在氢气存在的氛围中易发生逆向加氢反应，而转移脱氢路径刚好解决了该问题。转移脱氢法是向反应体系中加入氢受体，从而消耗醇脱氢过程中产生的氢气，但该技术对催化剂的要求比较高，既需要催化醇的脱氢过程，又要催化氢受体的加氢过程，且脱氢和加氢反应在同一体系中进行，其工艺条件难以匹配。
由前面论述可知，醇脱氢过程需要催化剂，而催化剂性能对该反应体系影响很大；根据催化剂的状态不同，可分为均相体系和非均相体系。均相催化体系中的催化剂一般活性和选择性较高，但需向体系中添加碱、有机溶剂和其它助剂，易造成设备腐蚀、催化剂难以分离和循环使用；而非均相体系刚好弥补了以上不足，同时具有环境友好性。在非均相体系中，常用的催化剂包括贵金属Pd、Pt、Ru及Au在载体上进行负载，载体包括金属氧化物、分子筛、碳材料和有机聚合物中的一种；或非贵金属Cu、Mn、Ni、Co、Cr及V的氧化物等。
传统的醇脱氢过程主要在固定床或流化床反应器中进行，产物氢气的生成会限制该可逆反应的正向进行。近年来膜反应器在脱氢方面的应用技术越发成熟，所谓的膜反应器是将反应与膜分离两个单独的过程相耦合, 在实现高效反应的同时, 实现物质的原位分离,使反应分离一体化。膜反应器最早应用于条件温和的生物反应过程中，主要采用的是有机膜材料，直到无机膜的出现，使得膜反应器在化工流程中的工业化应用成为可能。
醇脱氢膜反应器中采用的膜应具有氢气选择透过性，根据材料的不同，可分为致密膜和多孔膜。致密膜材料主要包括一些贵金属，如钯及钯合金，其对氢气具有接近100%的选择性，主要用于苯加氢制苯酚，亚硝酸盐加氢，烃类脱氢，水蒸气重整等加氢或脱氢反应，但其主要应用于气相反应，且对氢气的渗透率偏低，特别在反应温度较低的情况下；多孔膜的材料主要有二氧化硅、分子筛、碳和陶瓷等，只要严格控制孔径的大小，即可实现对氢气的高选择透过性，对于气相和液相反应均适用。
目前膜反应器虽然在脱氢方面有一定应用，但是主要集中在烃类脱氢、水蒸汽重整、水煤气变换等气相脱氢过程，而在醇液相脱氢方面的应用报道不多；此外，报道中的大部分案例都是将膜内反应产生的氢气渗透到膜外后用吹扫气吹走或抽真空，以加快渗透速率，这无疑增加额外的能耗和处理措施。而只有少数报道提到了对氢气的原位利用。
专利CN1164523A中提出一种利用Pb-陶瓷复合膜反应器进行气相催化脱氢，同时在渗透腔一侧进行氢氧的氧化反应，该过程虽然利用了氢氧反应为脱氢过程提供热量，但是Pb膜既作为于两边反应的催化剂也起到膜分离作用，其用量较大，必导致成本高，渗透率低，且Pb膜成型较难，因此其渗透速率和反应速率难以匹配使其达到较好的效果；且在氧化反应侧的反应速率和脱氢反应各点处的供热量无法控制；此外该专利采用的仅为单管反应，在实际应用中将会出现生产效率较低的问题。
在此基础上，专利CN1189483A则在该膜反应器的两侧反应腔内装填催化剂，分别进行气相催化脱氢和加氢耦合反应，其通过合理调节催化剂用量和膜面积的比值，以协调反应速率和渗透速率。而一般情况下，脱氢反应的温度会远高于加氢反应的温度，故两者的温度匹配是个很大的问题，且从脱氢反应侧渗透得到的氢气压力很低，而加氢反应需要较高压力才能进行，因此加氢侧的反应很难进行。
综上所述，目前采用膜反应器进行脱氢反应虽然比较常见，但是大多是针对气相脱氢反应，采用钯膜或钯合金膜，而此类膜对氢气的渗透率较低，且成本较高，成型困难，在液相反应中很难使用；此外，对于脱氢反应产生的氢气，大部分情况下都是用吹扫气吹走或抽真空，而没有充分利用，即使专利CN1189483A对产生的氢气进行加氢反应而实现热耦合，但没有考虑到工业放大过程中加氢和脱氢过程在反应条件上的不匹配，且对热耦合过程的控制几乎没有提及；另外，从工业应用的角度，如果采用目前报道的单管进行脱氢反应，则产率将很难提高，从而会影响到工厂的效益。
发明内容：
本发明的目的在于提供一种液相醇脱氢的列管式反应器及液相醇脱氢的方法，该液相醇脱氢的列管式反应器实现了可控的原位供热，大大提高了脱氢反应的转化率。
为实现上述目的，本发明采用的技术方案如下：
本发明液相醇脱氢的列管式反应器包括反应器壳体和间隔设置在所述反应器壳体内的若干个列管，所述列管的材质为气体选择渗透膜，所述气体选择渗透膜可透过氢气和氧气而不可透过液体分子；列管内设有脱氢催化剂，反应器壳体内的列管外设有氧化催化剂；所述列管的一端设有液相醇入口，所述列管的另一端设有脱氢产物出口；所述反应器壳体内还设有至少一根氧气膜管，氧气膜管的一端为氧气入口，氧气膜管的另一端封闭；反应器壳体上设有氧化产物出口。
本发明所述的液相醇脱氢的方法如下：在每根列管的膜内外两侧分别进行醇脱氢反应和氢气氧化反应，在脱氢反应侧，醇本身或者经溶剂溶解后的醇（若该醇在常温下为固态）进入预热器预热，达到一定温度后从列管的液相醇入口进入装填有脱氢催化剂的脱氢侧进行反应，目标产物从列管的脱氢产物出口采出运送到产品区；脱氢反应产生的氢气透过氢气选择渗透膜进入反应器壳体中，反应器壳体内装填有氧化反应的催化剂，氧气则定量通入列管中若干根专用的膜管内，通过选择渗透膜渗透到氧化侧与氢气发生氧化反应，产物水和剩余的氢气从反应器壳体的氧化产物出口采出。
对于部分需要进行溶解的醇原料（常温下为固态的醇），其溶剂包括苯，甲苯，二甲苯，对伞花烃等苯系溶剂中的一种，保证醇在液相状态下进行脱氢反应，而且该类溶剂在脱氢催化剂作用下不会发生脱氢反应。
所述的膜反应器所用的膜为列管式膜组件，在每根膜管的管程和壳程分别进行脱氢反应和氧化反应，并在相应的位置装填脱氢催化剂和氧化催化剂。
用于脱氢反应的催化剂包括贵金属Pd、Pt、Ru及Au在载体上进行负载，载体包括金属氧化物、分子筛、碳材料和有机聚合物中的一种；或非贵金属Cu、Zn、Mn、Ni、Co、Cr及V的氧化物中的一种，或多种的复合；采用的催化剂是以颗粒的形式填充于反应列管中。
由于脱氢采用液相反应，而生成的氢气和另一股进料氧气均为气相，很容易选择高透过性和高选择性的膜，所述的氢气和氧气气体选择渗透膜的材质为分子筛、二氧化硅、炭、陶瓷、多孔不锈钢或由上述材质中的两种或多种所构成的复合物，所选择的渗透膜为氢气和氧气均可透过，而液体分子不透过。
所述的列管中若干根氧气专用的膜管，其数量可以是一根或多根，材质同其它氢气选择膜管，半径可不同；专用膜管在列管中位置的选择原则是使反应器内各点的氧化侧供热值与脱氢侧的吸热值相匹配；采用该方法也进一步解决了氢气在氧化侧容易达到爆炸极限的问题。
所述的氧化反应为氢气和氧气生成水的气相反应，采用的催化剂是将金属铂负载于金属氧化物、分子筛、碳材料及水滑石等多孔介质中的一种；为了更好的控制反应器各点处氢气氧化反应的反应速率，在制备催化剂时通过控制金属铂的负载量或者装填部分惰性的负载材料来控制活性位点的数量，从而得到期望的催化剂活性。
通过催化氧化，使氢气氧化反应温度比加氢反应温度高50- 100℃，从而维持传热推动力；还可以控制加入膜管的氧气量和调整氧化催化剂的活性，以保证氧化反应侧的供热量与脱氢反应侧所需要的反应热相匹配，实现了原位的供热。以环己醇脱氢和氢气氧化的反应为例，其反应热如下所示:
（2）
（3）
由式（2）（3）可以看出，1mol氢气氧化产生的热量远高于醇脱氢产生1mol氢气所需的热量，因此可以通过控制氧化侧的氧气通量来调整氧化侧为脱氢侧提供的热量大小。
所述的液相醇脱氢反应的原料预热温度范围为100-450℃，反应的温度范围为150-500℃，压力范围为0.1-5MPa。
与现有技术相比，本发明申请有以下优点：
1）相比于专利CN1164523A中采用的氧气进料方式，本申请提出的通过选择性膜管进料氧气的方法，其优势在于氧气渗透到氧化侧更均匀，再加上在不同位置填充不同量或不同活性（制备不同铂的负载量来实现）的氧化催化剂，从而避免出现反应器内各位置供热量不可控的现象，可以达到反应器内各点的供热量和吸热量的良好匹配；此外采用该方法进行氧气进料也进一步解决了氢气在氧化侧容易达到爆炸极限的问题。
2）由于脱氢采用液相反应，而生成的氢气和另一股进料氧气均为气相，在进行膜材质选择的时候可选范围很广，而且容易实现高透过性和高选择性；本发明采用的膜优选为多孔无机膜，目前研究普遍采用的钯膜多用于气相催化过程，且渗透率不佳，成本高，难成型，而多孔无机膜通过合理设计其孔径，即可达到良好的氢气和氧气选择透过性，工业上制作成本较低，容易成型。
3）大部分的醇脱氢反应为可逆反应，其平衡转化率不高，根据可逆反应的原则，当产物氢气从体系中移走后可促进脱氢反应的正向进行，因此采用具有氢气选择透过性的膜可将产物氢气移走，提高脱氢反应的转化率，从而提高羰基化合物的产量；在氧化侧将氢气反应后，将有利于降低氢气分压，提高膜内氢气渗透的推动力。
4）采用膜反应器进行醇脱氢反应，该反应所需的热量由氢气在氧化侧的催化氧化提供，相对于燃烧来说，其温度低，容易控制，且由于氢气氧化产热量远高于脱氢吸热量，因此工业上可通过控制加入氧化侧的氧气量和改变催化剂活性，为脱氢反应提供所需的热量，保证了原位供热，减少了能耗；同时氧化侧的产物为氢气和水的混合流股，经过简单除水后的氢气即可回收用于其它过程。
5）在膜的两侧分别采用不同的催化剂，可保证脱氢反应的速率及选择性，相比于采用具有催化作用的膜，本方法能更好地控制脱氢反应进程；此外，在该反应器的膜内外分别进行液相的脱氢反应和气相的氧化反应，在工业上是比较容易实现的。
6）脱氢反应膜反应器所用的膜为列管式膜组件，从工业应用来看，与单管膜反应器相比，其生产的效率更高，结构更紧凑，且集双功能于一体：既可以作为反应器，也同时作为脱氢反应和氧化反应的换热器。
附图说明：
图1是本发明的列管式膜反应器结构简图；
图2是图1的剖面图；
图3为反应器内单根膜管的结构示意图。
具体实施方式：
为详细说明本发明的技术内容、构造特征、所实现目的及效果，以及结合实施方式并配合附图详细说明。
本发明液相醇脱氢的列管式反应器及其使用方法如下：
本发明液相醇脱氢的列管式反应器包括反应器壳体1和间隔设置在所述反应器壳体内的若干个列管2，所述列管2的材质为气体选择渗透膜，所述气体选择渗透膜可透过氢气和氧气而不可透过液体分子；列管内设有脱氢催化剂，列管外且位于反应器壳体内设有氧化催化剂；所述列管的一端设有液相醇入口3，所述列管的另一端设有脱氢产物出口4；所述反应器壳体内还设有一个或多个氧气膜管5，氧气膜管5的一端为氧气入口6，氧气膜管的另一端封闭；反应器壳体底部上设有氧化产物出口7。
本发明液相醇脱氢的方法如下：在列管2的膜内外两侧分别进行醇脱氢反应和氢气氧化反应。在脱氢反应侧，醇本身或者经溶剂溶解后的醇（若该醇在常温下为固态）进入预热器预热，达到一定温度后从列管2的液相醇入口3进入装填有脱氢催化剂的脱氢侧进行反应，目标产物从脱氢产物出口4采出运送到产品区；脱氢反应产生的氢气透过氢气选择渗透膜进入反应器壳体1内，该侧装填有氧化反应的催化剂，氧气则从进口6定量通入列管中若干根专用的氧气膜管5内，通过选择渗透膜渗透到反应器壳体1内与氢气发生氧化反应，产物水和剩余的氢气从反应器壳体1设置的氧化产物出口7采出。
对于部分需要进行溶解的醇原料（常温下为固态的醇），其溶剂包括苯，甲苯，二甲苯，对伞花烃等苯系溶剂中的一种，保证醇在液相状态下进行脱氢反应，而且该类溶剂在脱氢催化剂作用下不会发生脱氢反应。
所述的膜反应器所用的膜为列管式膜组件，在每根膜管的管程和壳程分别进行脱氢反应和氧化反应，并在相应的位置装填脱氢催化剂和氧化催化剂。
用于脱氢反应的催化剂包括贵金属Pd、Pt、Ru及Au在载体上进行负载，载体包括金属氧化物、分子筛、碳材料和有机聚合物中的一种；或非贵金属Cu、Zn、Mn、Ni、Co、Cr及V的氧化物中的一种，或多种的复合；采用的催化剂是以颗粒的形式填充于反应列管中。
由于脱氢采用液相反应，而生成的氢气和另一股进料氧气均为气相，很容易选择高透过性和高选择性的膜，所述的氢气和氧气气体选择渗透膜的材质为分子筛、二氧化硅、炭、陶瓷、多孔不锈钢或由上述材质中的两种或多种所构成的复合物，所选择的渗透膜为氢气和氧气均可透过，而液体分子不透过。
所述的列管中若干根氧气专用的膜管，其数量可以是一根或多根，材质同其它氢气选择膜管，半径可不同；专用膜管在列管中位置的选择原则是使反应器内各点的氧化供热值与脱氢吸热值相匹配；采用该方法也进一步解决了氢气在氧化侧容易达到爆炸极限的问题。
所述的氧化反应为氢气和氧气生成水的气相反应，采用的催化剂是将金属铂负载于金属氧化物、分子筛、碳材料及水滑石等多孔介质中的一种；为了更好的控制反应器各点处氢气氧化反应的反应速率，在制备催化剂时通过控制金属铂的负载量或者装填部分惰性的负载材料来控制活性位点的数量，从而得到期望的催化剂活性。
通过催化氧化，使氢气氧化反应温度比加氢反应温度高50- 100℃，从而维持传热推动力；还可以控制加入膜管的氧气量和调整氧化催化剂的活性，以保证氧化反应侧的供热量与脱氢反应侧所需要的反应热相匹配，实现了原位的供热。
所述的液相醇脱氢反应的原料预热温度范围为100-450℃，反应的温度范围为150-500℃，压力范围为0.1-5MPa。
实施例1
本案例中，在膜反应器内进行的是液相异龙脑脱氢制备樟脑的反应。本案例中的异龙脑为工业级原料，由于异龙脑常温下为固体粉末，因此先将其溶解于二甲苯后形成质量分数为30%的溶液，该溶液的质量反应空速为0. 5h-1，经过换热器加热达到预热温度220℃后进入膜反应器的管程进行脱氢反应，管程中装填的是由日本NGC公司生产的GC250 型Cu-Zn-Al催化剂，并采用热电偶套管对其中任意一根脱氢反应管的床层温度进行轴向布点测量；氧气通过流量计量后通入列管中心的氧气专用膜管内，氧气透过膜向壳程渗透并与氢气发生氧化反应，氧气和异龙脑的摩尔比为1:6，壳程中装填的是采用多次涂层-浸渍法制备的负载型Pt/Al2O3氧化催化剂，其中Pt的负载质量分数约为1%；在脱氢反应侧的压力为0.6MPa，反应温度为220℃；反应器采用的膜是由Sulzer Chemtech生产的二氧化硅膜系统（SMS），每根管的内径8mm，外径14mm；脱氢侧的目标产物樟脑和溶剂二甲苯的混合物进入溶剂回收工段进行溶剂回收循环利用，樟脑产品则送至成品区。
以上案例中所测得的稳定后床层温度如下表所示（表中“测温布点”的数字来源于图3）：
测温布点 1 入口 2 3 4 5 出口
温度/℃ 220 218 221 220 221
将以上案例的实验结果与目前采用其它工艺的数据进行对比，结果如下：
催化剂 反应温度/℃ 转化率/% 选择性/%
本案例 GC250 220 99.56 99.78
文献值* 锌-钙型催化剂 295 99.20 97.00
文献值*：来源于专利CN1027755C：林允隆等，异龙脑气相脱氢制樟脑。
从以上对比结果可以看出，采用本申请的方法进行异龙脑脱氢反应，不仅转化率和选择性较高，而且由于采用管式结构和原位供热系统，其轴向的床层温度更均一，且设备简单，紧凑，生产效率高。
实施例2
本案例中，在膜反应器内进行的是液相环己醇脱氢制备环己酮的反应。将环己醇原料经过换热器加热达到预热温度220℃后进入膜反应器的管程进行脱氢反应，环己醇的反应空速为1.0h-1，管程中装填的是由南京化学工业有限公司研究院研制开发的Cu-Zn双组分脱氢催化剂DH021，并采用热电偶套管对其中任意一根脱氢反应膜管的床层温度进行轴向布点测量；氧气通过计量器计量后列管中心的氧气专用膜管内，氧气透过膜向壳程渗透并与氢气发生氧化反应，氧气和环己醇的摩尔比为1:8，壳程中装填的是采用多次涂层-浸渍法制备的负载型Pt/Al2O3氧化催化剂，其中Pt的负载质量分数约为1%；在脱氢反应侧的压力为0.5MPa，反应温度为220℃；反应器采用的膜是由由Sulzer Chemtech生产的二氧化硅膜系统（SMS），每根管的内径8mm，外径14mm；反应产物环己酮送至成品区。
以上案例中所测得的稳定后床层各点温度和文献值如下表所示（表中本案例的“温度布点”数字来源于图3）：
测温布点 设定值 1 入口 2 3 4 5 出口
本案例/℃ 220 220 218 220 220 222
文献值*/℃ 240 237 242 240 240 242
文献值*：来源于文献：周小文等，两种环己醇脱氢催化剂的稳定性比较。
将以上案例的实验结果与目前工业上采用其它工艺的数据进行对比，结果如下：
催化剂 反应温度/℃ 转化率/% 选择性/%
本案例 DH021 220 90.26 99.56
文献值1* DH021 230 55.50 99.33
文献值2* GC250 230 47.77 99.01
文献值3* LYT-96 230 52.40 99.98
文献值1*，文献值2*：南京帝斯曼东方化工有限公司的数据；文献值3*：湖南鹰山石化总厂的数据；均来源于文献：孙烽等人，几种环己醇脱氢催化剂性能的比较。
从以上结果可以看出，采用本申请的方法进行环己醇脱氢反应，不仅转化率和选择性较高，而且由于采用管式结构和原位供热系统，其轴向的床层温度更均一，且设备简单，紧凑，生产效率高。
以上所述仅为本发明的较佳实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所做的等效变换，或直接或间接运用在其它相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (6)

1.一种液相醇脱氢的列管式反应器，其特征在于：包括反应器壳体和间隔设置在所述反应器壳体内的若干个列管，所述列管的材质为气体选择渗透膜，所述气体选择渗透膜可透过氢气和氧气而不可透过液体分子；列管内设有脱氢催化剂，反应器壳体内的列管外设有氧化催化剂；所述列管的一端设有液相醇入口，所述列管的另一端设有脱氢产物出口；所述反应器壳体内还设有至少一根氧气膜管，氧气膜管的一端为氧气入口，氧气膜管的另一端封闭；反应器壳体上设有氧化产物出口；所述气体选择渗透膜的材质为二氧化硅，所述脱氢催化剂以颗粒形式装填于列管内，所述脱氢催化剂为负载在载体上的贵金属Pd、Pt、Ru或Au，所述载体为金属氧化物、分子筛、碳材料或有机聚合物；所述脱氢催化剂还为非贵金属Cu、Zn、Mn、Ni、Co、Cr或V，所述氧化催化剂为将金属铂负载于多孔介质上，所述多孔介质为金属氧化物、分子筛、碳材料或水滑石。
2.根据权利要求1所述的液相醇脱氢的列管式反应器，其特征在于：氧气膜管的位置选择遵循的原则是使反应器内各点的氧化侧供热值与脱氢侧吸热值相匹配。
3.一种将权利要求1或2所述的列管式反应器用于液相醇脱氢过程的方法，其特征在于：包括如下步骤：
将预热后的液相醇通入反应器中列管的液相醇入口，在管内进行脱氢反应，并从脱氢产物出口获取脱氢产品；以预设通入量或通入速率将氧气输入反应器中氧气膜管的入口，氧气从管内渗透到反应器壳体内，与氢气发生氧化反应，并从反应器壳体设置的氧化产物出口采出水和未反应的氢气；所述液相醇包括常温下为液相的醇或常温下为固相的溶于溶剂的醇，所述溶剂在脱氢催化剂作用下可保持稳定；所述溶剂为苯、甲苯、二甲苯或对伞花烃。
4.根据权利要求3所述将列管式反应器用于液相醇脱氢过程的方法，其特征在于：控制所述氧化反应的温度比脱氢反应的温度高50-100℃。
5.根据权利要求3所述将列管式反应器用于液相醇脱氢过程的方法，其特征在于：通过控制氧气通入量、氧气通入速率或氧化催化剂的活性使氧化反应的供热量与脱氢反应所需的热量相匹配；所述控制氧化催化剂的活性的方法包括控制金属铂的负载量或在催化剂中掺杂惰性载体。
6.根据权利要求3所述将列管式反应器用于液相醇脱氢过程的方法，其特征在于：脱氢反应的液相醇预热温度范围为100-450℃，反应的温度范围为150-500℃，压力范围为0.1-5MPa 。
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