CN101284756A - 碳氢化合物中HBr的净化方法 - Google Patents
碳氢化合物中HBr的净化方法 Download PDFInfo
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Abstract
本发明公开一种从碳氢化合物(烯烃、芳烃和/或烷烃)中脱出HBr净化碳氢化合物的方法。该方法采用一种硅胶负载金属氧化物的固体材料(Mox/SiO2,MOx=MgO、CoO、Co2O3和CuO以及它们的混合物)吸收碳氢化合物中HBr,可以使其中的HBr含量降低到1.87×1016mol/L以下,然后将吸收了HBr的固体材料在空气中或氧气中氧化后再生出MOx/SiO2并回收Br2,实现连续净化碳氢化合物的目的。
Description
技术领域
本发明公开一种从碳氢化合物中分离HBr的方法,尤其是从烯烃中分离回收HBr。属于碳氢化合物中HBr的化学吸收分离技术领域。
背景技术
在本领域的研究中,由于一般没有从碳氢化合物中分离HBr的需求,所以没有见到类似的报道和相关专利。在我们近年来的研究中,我们设计了把甲烷等低碳烃转化成碳氢化合物尤其是烯烃等产品的新流程[申请号为200610031377.9的中国专利],两步流程如反应(A)和(B)所示:
第一步,低碳烃如甲烷,在催化剂A上首先与HBr/H2O和氧气反应生成溴代烃:
第二步,溴代烃再在催化剂B上可以被有效地转化成烯烃、芳烃、烷烃(少量)等高碳烃和HBr。前期的研究工作表明,溴代烃的转化率可达99%以上。反应式如下:
n,m,x=2,3,4,5,6,7,8,9,10,11,12,13
在制烯烃、芳烃和烷烃的反应(B)中都有HBr的生成。这些产物中大量的HBr先用常规方法进行粗洗,比如用第一步反应(A)以后的稀HBr溶液进行粗洗,HBr循环使用。但是粗洗后产物中仍残余有HBr,因烯烃等化合物都有Lewis碱性,采用常规的分离方法,是不能把HBr从烯烃和芳烃类化合物中很好分离出来的,同时也难于纯化烯烃和芳烃类化合物。
发明内容
本发明公开了从一种碳氢化合物中分离HBr的净化方法,其特征在于所述的碳氢化合物为烯烃、芳烃和烷烃。
在本发明的净化方法中,含HBr的碳氢化合物与一种硅胶负载金属氧化物的固体材料(MOx/SiO2)接触,与HBr反应,吸收了碳氢化合物中的HBr并且生成相应的金属溴化物,然后固体材料中的溴化物经过与氧气或空气中的氧气反应,再生载体上的金属氧化物并且回收Br2。
在这一分离过程中,含HBr的碳氢化合物首先通过一个装填有MOx/SiO2的容器在一定温度(100至600℃)下进行流过式接触,金属氧化物MOx选择性地与HBr反应生成不挥发的金属溴化物和水,以达到净化碳氢化合物的目的;在MOx/SiO2吸收HBr达到饱和时把含HBr的碳氢化合物物料切换到另一个切换到装填有MOx/SiO2的容器继续进行同样的操作;而已经吸收有HBr的装填有MOx/SiO2的容器经过水蒸汽吹扫后通人空气或氧气在一定温度(250~600℃)下再生其中的金属氧化物MOx并且回收溴,这样两个或两个以上的装填有MOx/SiO2的并列容器通过净化-再生循环操作就可以达到连续净化碳氢化合物和回收溴的目的。
在本发明的净化容器中装填的MOx/SiO2是采用硅胶为载体负载MgO、CoO、Co2O3和CuO以及它们的混合物。其中硅胶是市售商品硅胶以及从含硅前体如硅酸盐、SiCl4和硅元酸酯水解制备,然后再把金属Mg、Co和Cu的的醋酸盐、硝酸盐、溴化物等可溶性盐的水溶液浸泡载体硅胶,然后烘干焙烧制成需要的MOx/SiO2固体材料。
在进行HBr的吸收操作时,碳氢化合物中的HBr在与MOx/SiO2进行接触时与MOx/SiO2中的金属氧化物MOx(MgO、CoO、Co2O3和CuO以及它们的混合物)的反应一般在100至600℃进行,较好的反应温度范围是150至400℃,最好的反应温度范围是在170至300℃之间。在吸收了HBr后MOx/SiO2的再生一般是在250至600℃之间进行,较好的再生温度范围是300至500℃,最好的再生温度是在320至450℃之间。
采用本发明的方法净化含HBr的碳氢化合物时,整个净化***一般由两个至八个装填有MOx/SiO2的容器通过切换阀连接。每个装填有MOx/SiO2的容器可以是一个柱体形状的两端与切换阀相连接的固定床净化塔。在净化过程中每个都是通过两端的切换阀切换到净化、吹扫、再生和吹扫四个步骤完成每一个操作循环的。在固定床净化塔处于吸收操作阶段时,净化塔进口处切换阀切换到含HBr的碳氢化合物物料,净化塔出口处切换阀切换到碳氢化合物储罐。在吸收HBr接近饱和时,床层中的碳氢化合物需要以水蒸汽吹扫后才能通氧气或空气再生,所以接下去进入吹扫操作阶段。在固定床净化塔处于吹扫操作阶段时,净化塔进口处切换阀切换到水蒸汽,出口切换到一个气液分离器,气液分离器出口与含HBr的碳氢化合物物料管连接。在吹扫出残留的碳氢化合物后,可以进入再生操作阶段。在再生操作阶段净化塔进口处切换阀切换到空气或氧气供给***,净化塔出口处切换阀切换到Br2收集储罐。在再生操作完成以后,由于***中有氧气,所以不能立即进入下一个净化操作,必须先进行吹扫,吹出器中的氧气以后才能进行一个净化操作,在此吹扫操作中净化器进口处切换阀切换到水蒸汽,出口切换到放空状态,从这个操作过程可以看出,对于每一个净化器,它的操作都不是连续的,为了保证连续净化含HBr的碳氢化合物,通常采用两个或两个以上同样的净化塔。当其中的一个处于吸收操作时,其它净化塔同时在进行其它三个操作,从而使分离操作连续进行。
实施例
金属氧化物/硅胶(MOx/SiO2的制备
硅胶载体制备
SiO2可以使用市场上购买的硅胶,或从SiCl4和硅元酸酯水解制备。在制备SiO2时,把120.0ml的SiCl4或Si(OC2H5)4加入800ml水中在室温下搅拌12小时得到含水硅胶样品,含水硅胶在120℃干燥6小时,然后在450℃烧4小时得硅胶SiO2,制成40至60目的颗粒备用。
MOx/SiO2的制备
称取20.00克上面制备的40至60目的硅胶和99.25mmol的M的醋酸盐、硝酸盐、溴化物等可溶性盐在搅拌下加入100ml去离子水中在室温下放置2小时,然后在120℃干燥6小时,最后在450℃空气中烧4小时降温至室温后得MOx/SiO2,制成40至60目的颗粒备用。
制成的MOx/SiO2固体材料中金属氧化物MOx,包括MgO、CoO、Co2O3和CuO以及它们的混合物。
碳氢化合物的净化
需要净化的气体组成为
A气体:丙烯
B气体:甲烷(>75%)、异丁烯(10.0%)、丙烯(1.0%)、环戊烯(6.0%)、环己烷(3.0%)、苯(2.0%)、甲苯(1.0%)和二甲苯(2.0%)的混和气。
在净化A气体时,以3.0ml/hour的速度把40wt%HBr/H2O溶液泵入一个填有石英沙并且加热到200℃的石英管中,丙烯以5.0ml/min的流量同时通人这个加热的石英管,在管的流出口连接一个气液分离器,气体出口得到的气体就是含有HBr的混合气。流出气鼓泡经过AgNO3(4.0M,5.0ml)溶液,从溶液增重量测定HBr在丙烯中的浓度。HBr在丙烯中的浓度为5.3%(mol)。这个混合气体通入一个装有10.0克MgO/SiO2的加热到200℃的净化管,硫出的气体用AgNO3溶液(5.0ml,4.0M)检测HBr的流出,通常在10至12.5小时发现AgBr生成此时净化管中的材料吸收HBr达到饱和,记录流过的丙烯体积得净化量。在把净化管中的气体从HBr/C3H6切换到水蒸汽吹扫5分钟,用空气或氧气在320至450℃再生净化管中的材料,到没有溴流出时,切换到水蒸汽吹扫5分钟,进行下一循环操作。
在操作三次以后,材料达到稳定状态,此时每克MgO/SiO2可以净化0.375升丙烯,约吸收0.1克HBr,在AgNO3溶液中出现AgBr时,溶液中Br-离子的浓度为1.4×10-13M,5.0ml的AgNO3溶液(4.0M)有7.0×10-16mol的Br-离子。而这些Br-离子是由3.75升丙烯带来的,所以残留在丙烯中的HBr浓度应该小于1.87×10-16mol/升。
采用B气体重复以上实验得到同样的结果。
Claims (14)
1、本发明公开了一种含HBr的碳氢化合物的净化方法,包括以下步骤:
1)含HBr的碳氢化合物首先通过一个装填有金属氧化物/载体固体材料的容器在一定温度下进行流过式接触,固体材料中的金属氧化物选择性地与HBr反应生成金属溴化物和水,流出的碳氢化合物收集在储罐中实现净化操作;
2)在金属氧化物/载体固体材料吸收HBr达到饱和时,把含HBr的碳氢化合物物料切换到另一个装填有相同金属氧化物/载体固体材料的容器继续进行同样的净化操作,而已经吸收有HBr的装填有金属氧化物/载体固体材料的容器经过水蒸汽吹扫后,通人氧在一定温度下再生其中的金属氧化物并且回收溴,以备下一循环净化使用;
3)两个或两个以上的装填有金属氧化物/载体固体材料的容器通过切换阀连接成一个净化***,经过净化-再生循环操作达到连续净化碳氢化合物和回收溴的目的。
2、根据权利要求1所说的含HBr碳氢化合物的净化方法,其特征在于碳氢化合物是烷烃、烯烃和芳烃。
3、根据权利要求1所说的含HBr碳氢化合物的净化方法,其特征在于金属氧化物/载体固体材料含有一种金属氧化物有效成分和一种载体。
4、根据权利要求3所说的金属氧化物有效成分,其特征在于金属氧化物有效成分是MgO、CoO、Co2O3和CuO以及它们的混合物。
5、根据权利要求3所说的载体,其特征在于载体是硅胶载体。
6、根据权利要求5所说的硅胶载体,其特征在于硅胶载体是市售商品硅胶或从含硅前体如硅酸盐、SiCl4和硅元酸酯制备的硅胶。
7、根据权利要求4所说的金属氧化物有效成分,其特征在于金属氧化物有效成分MgO、CoO、Co2O3和CuO及其混合物是由它们的醋酸盐、硝酸盐和溴化物的水溶液浸泡载体,然后烘干焙烧制成的并且负载于硅胶载体上的金属氧化物。
8、根据权利要求1所说的含HBr的碳氢化合物的净化方法,其特征在于碳氢化合物中的HBr在与金属氧化物/载体固体材料进行接触时与其中的金属氧化物(MgO、CoO、Co2O3和CuO)反应生成不挥发的金属溴化物,从而达到HBr与碳氢化合物分离的目的。
9、根据权利要求1中步骤1)所说的碳氢化合物的净化方法,其特征在于碳氢化合物中的HBr与固体材料中的金属氧化物(MgO、CoO、Co2O3和CuO)的反应是在100至600℃进行的,较好的反应温度范围是150至400℃,最好的反应温度范围是在170至300℃之间。
10、根据权利要求1中步骤2)所说的含HBr的碳氢化合物的净化方法,其特征在于金属氧化物/载体固体材料吸收了HBr以后生成的金属溴化物是用氧气或空气氧化再生的,在再生固体材料的同时回收溴。
11、根据权利要求10所说的固体材料的再生,其特征在于固体材料的再生是在250至600℃进行的,较好的温度范围是300至500℃之间,最好的反应温度范围是在320至450℃之间。
12、根据权利要求1中步骤3)所说的净化***,其特征在于整个净化***由两个至八个装填有金属氧化物/载体固体材料的容器通过切换阀连接而成的。
13、根据权利要求12所说的净化***,其特征在于每个装填有金属氧化物/载体固体材料的容器是一个柱体形状的两端与切换阀相连接的固定床净化塔。
14、根据权利要求12所说的净化***,其特征在于每个装填有金属氧化物/载体固体材料的容器都是通过两端的切换阀切换到净化、吹扫、再生和吹扫四个步骤完成每一个操作循环的。
Priority Applications (4)
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CNA2007100347271A CN101284756A (zh) | 2007-04-13 | 2007-04-13 | 碳氢化合物中HBr的净化方法 |
US12/595,781 US20100135895A1 (en) | 2007-04-13 | 2008-04-14 | Process for Purifying HBr in Hydrocarbons |
EP08733968A EP2147908A1 (en) | 2007-04-13 | 2008-04-14 | A PROCESS FOR PURIFYING HBr IN HYDROCARBONS |
PCT/CN2008/000770 WO2008125016A1 (fr) | 2007-04-13 | 2008-04-14 | Procédé de purification du hbr présent dans des hydrocarbures |
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CNA2007100347271A CN101284756A (zh) | 2007-04-13 | 2007-04-13 | 碳氢化合物中HBr的净化方法 |
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US (1) | US20100135895A1 (zh) |
EP (1) | EP2147908A1 (zh) |
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WO (1) | WO2008125016A1 (zh) |
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CN104829411A (zh) * | 2015-05-15 | 2015-08-12 | 南京工业大学 | 一种微通道反应器中连续制备对二甲苯的方法 |
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US5914455A (en) * | 1997-09-30 | 1999-06-22 | The Boc Group, Inc. | Air purification process |
US6472572B1 (en) * | 2001-06-20 | 2002-10-29 | Grt, Inc. | Integrated process for synthesizing alcohols and ethers from alkanes |
US6486368B1 (en) * | 2001-06-20 | 2002-11-26 | Grt, Inc. | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
RU2004125653A (ru) * | 2002-01-24 | 2006-01-20 | Джи Ар Ти, ИНК. (US) | Интегрированный способ синтеза спиртов, простых эфиров и олефинов из алканов |
US7064238B2 (en) * | 2004-01-02 | 2006-06-20 | Marathon Oil Company | Conversion of alkanes to oxygenates |
US20060100469A1 (en) * | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
EP1632467A1 (en) * | 2004-09-06 | 2006-03-08 | Research Institute of Petroleum Industry | Improved catalyst for direct conversion of methane to ethane and ethylene |
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CN104829411A (zh) * | 2015-05-15 | 2015-08-12 | 南京工业大学 | 一种微通道反应器中连续制备对二甲苯的方法 |
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US20100135895A1 (en) | 2010-06-03 |
EP2147908A1 (en) | 2010-01-27 |
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