CN104549122B - 常温脱硫脱砷剂及其制备方法 - Google Patents
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Abstract
本发明涉及常温脱硫脱砷剂及其制备方法,主要解决现有技术中脱硫脱砷剂堆密度高,硫容和砷容低的问题。本发明通过采用一种脱硫脱砷剂,以重量份数计,包括以下组分:a)1~10份的绿铜锌矿;b)10~50份的氧化铜;c)10~60份的氧化锌;d)0.01~1份的过渡金属Rh、Pt、Pd、Ag、Au中的至少一种的技术方案,较好地解决了该问题,可用于天然气、合成气、轻质气液态烃类等的净化中。
Description
技术领域
本发明涉及一种常温脱硫脱砷剂及其制备方法。
背景技术
硫砷等杂质广泛存在于天然气、合成气、煤制气、轻质气液态烃类等原料中,这些杂质的存在会导致很多催化剂中毒失活,大大缩短催化剂寿命,甚至导致催化反应无法正常进行;此外,未脱除干净的硫砷杂质会随着生产的进行进入下游合成品中,从而带来一系列的环境健康等方面的问题。因此,高效高精度地脱除硫砷等杂质对于保护下游装置的主催化剂且同时提高下游产品的品质有着非常重要的意义。
一般情况下,在工业原料中存在的含硫物质主要是H2S和COS,对于这些含硫物质的深度脱除效果最好的是氧化锌脱硫剂。氧化锌脱硫以其脱硫精度高、使用便捷、稳妥可靠、硫容量高、起着“把关”和“保护”作用而占据非常重要的地位,它广泛的应用在合成氨、制氢、煤化工、石油精制、饮料生产等行业,以脱除天然气、石油馏分、油田气、炼厂气、合成气、二氧化碳等原料中的硫化氢及某些有机硫。硫化锌脱硫可将原料气中的硫脱除至0.055mg/kg。常温氧化锌脱硫剂中添加CuO以提高其脱硫能力。氧化锌脱硫剂一般用于精脱硫过程,它也能吸收一般的有机硫化合物。工业原料中的砷杂质,通常以AsH3形式存在,工业上使用的脱砷剂大致可分成铜系、铅系、锰系和镍系四类,其中以铜系较为常见。铜系脱砷剂砷容高,可在常温、常压及较高空速下进行。铜系脱砷剂又可分成金属铜、CuO-Al2O3、CuO-ZnO-Al2O3等。当以CuO为活性组分时,AsH3将Cu2+还原为低价或金属态,砷与铜结合或游离成元素态。脱硫剂和脱砷剂的发展趋势是向低堆密度、低使用温度、高强度以及高硫容和砷容的方向发展。
专利CN101591554A公开了一种常温复合脱硫脱砷剂及其制备方法,该脱硫脱砷剂由载体和活性组分组成,活性组分为氧化铅、磁性氧化铁及氧化铜,载体为γ-Al2O3,该脱硫脱砷剂需要在350~650℃活化4~8小时,从其组成及制备方法可以看出,该氧化物脱硫脱砷剂堆密度高,制备过程复杂,工业应用成本较高。
专利CN102049236A公开了一种铜锌常温脱硫剂及其制备方法,该脱硫剂是由碱式碳酸锌、碱式碳酸铜和粘结剂组成,该脱硫硫剂的制备是将市售的碱式碳酸锌、碱式碳酸铜、粘结剂和水进行捏合、成型、干燥后得到,该脱硫剂通过物理混合得到,因而其中的锌铜活性组分无法发挥协同作用,从而导致其硫容较低。
发明内容
本发明所要解决的技术问题是现有技术中脱硫脱砷剂堆密度高,硫容和砷容低的问题,提供一种新的脱硫脱砷剂及其制备方法。该脱硫脱砷剂含有绿铜锌矿及CuO-ZnO类固溶体,具有堆密度低,硫容和砷容高的优点。
为解决上述技术问题,本发明采用的技术方案如下:通过一种脱硫脱砷剂,以重量份数计,包括以下组分:a) 1~10份的绿铜锌矿;b) 10~50份的氧化铜;c) 10~60份的氧化锌;d) 0.01~1份的过渡金属Rh、Pt、Pd、Ag、Au中的至少一种。
上述技术方案中,以脱硫脱砷剂重量份数计,所述绿铜锌矿的优选范围为2~8份;所述氧化铜的优选范围为13~48份;所述氧化锌锌的优选范围为15~55份;所述过渡金属的优选范围0.1~0.5份;过渡金属优选方案为Rh或Ag的至少一种;脱硫脱砷剂堆密度小于1.0kg/m3,侧压强度大于70N/粒。
所述常温脱硫脱砷剂的制备方法,依次包括如下步骤:
(1) 将硝酸铜、硝酸锌、硝酸铝、含有过渡金属M(Rh、Pt、Pd、Ag、Au)中至少一种的水溶性无机盐和水按摩尔比计:Cu/Zn为0.1~2;Al/Zn为0~0.8;M/(Cu+Zn+Al)为0.001~0.1;(Cu+Zn+Al+M)/H2O为0.01~0.04的比例混合,搅拌均匀得溶液Ⅰ;
(2) 将碳酸钠、碳酸氢钠、碳酸铵中的至少一种和水按摩尔比为0.01~0.04的比例混合,搅拌均匀得溶液Ⅱ;
(3) 将溶液Ⅰ和Ⅱ混合均匀,在40~90℃,反应0.5~3小时得沉淀物,将沉淀物洗涤干燥;
(4) 将沉淀物、粘结剂、润滑剂混合碾压均匀,加入10~50重量%的水,造粒;
(5) 将造粒好的粉料在170~300℃,焙烧1~5小时;
(6) 压片成型为脱硫脱砷剂。
上述技术方案中,步骤(4)中加入的水量是以沉淀物、粘结剂和润滑剂的总重量为基准的。
本发明所述常温脱硫脱砷剂,由于含有绿铜锌矿,其体积较大,在堆积过程中会产生较大的孔道,因而其堆密度较低。绿铜锌矿热处理后形成的CuO-ZnO类固溶体,该类固溶体中CuO周围排布较多ZnO,同理,ZnO周围也排布了较多的CuO,可以保证CuO和ZnO充分细化,使得CuO颗粒和ZnO颗粒界面接触的机会大大增加,提供更多的活性中心。该脱硫脱砷剂加入过渡金属,有效提高了脱硫脱砷剂的硫容和砷容。本发明取得了较好的技术效果。
本发明所述常温脱硫脱砷剂可用于天然气、合成气、轻质气液态烃类等的净化中。在常温、常压、体积空速为3000h-1的条件下,以含不同浓度硫、砷化合物杂质的氮气或合成气通过反应器,吸附剂的硫容可达20%以上。在常温、压力为3.0MPa、质量空速为3.5h-1的条件下,以含不同浓度硫、砷化合物杂质的液态丙烯通过反应器,吸附剂的硫容也可达20%以上。
下面通过实施例对本发明作进一步的阐述。
附图说明
图1是制备吸附剂的XRD衍射谱图。(绿铜锌矿的特征衍射峰在2θ=13.0±0.2°;氧化铜的衍射峰在2θ=35.49±0.2°和38.73±0.2°;氧化锌的特征衍射峰在2θ=31.8±0.2°,36.2±0.2°和56.6±0.2°)
具体实施方式
【比较例1】
比较例1合成样品为氧化锌。
将硝酸锌40千克,硝酸铝10千克,硝酸银0.1千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,300℃焙烧3小时,压片成型,得到样品组成见表1。
【比较例2】
比较例2合成样品为氧化铜。
将硝酸铜30千克,硝酸铝10千克,硝酸银0.1千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,300℃焙烧3小时,压片成型,得到样品组成见表1。
【比较例3】
比较例3合成样品为不含绿铜锌矿的氧化铜氧化锌。
将硝酸铜30千克,硝酸锌40千克,硝酸铝10千克,硝酸银0.1千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,350℃焙烧5小时,压片成型,得到样品组成见表1。
【实施例1】
将硝酸铜30千克,硝酸锌40千克,硝酸铝10千克,硝酸银0.1千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例2】
将硝酸铜20千克,硝酸锌50千克,硝酸铝10千克,氯化铑0.2千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在60℃反应2小时,将沉淀物洗涤干燥,而后加入5千克氧化铝,1千克石墨混合碾压,而后加入35重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例3】
将硝酸铜10千克,硝酸锌60千克,硝酸铝10千克,硝酸银0.2千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在60℃反应2小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入50重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例4】
将硝酸铜40千克,硝酸锌30千克,硝酸铝10千克,硝酸银0.2千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸铵26千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在80℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入40重量%的水,造粒,250℃焙烧5小时,压片成型,得到样品组成见表1。
【实施例5】
将硝酸铜30千克,硝酸锌40千克,硝酸铝10千克,硝酸银0.2千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例6】
将硝酸铜30千克,硝酸锌40千克,硝酸铝10千克,硝酸银0.6千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例7】
将硝酸铜30千克,硝酸锌40千克,硝酸铝10千克,硝酸银1千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例8】
将硝酸铜30千克,硝酸锌40千克,硝酸铝10千克,硝酸银2千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例9】
将硝酸铜30千克,硝酸锌40千克,硝酸铝10千克,硝酸银0.1千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,280℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例10】
将硝酸铜30千克,硝酸锌40千克,硝酸铝10千克,硝酸银0.1千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,290℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例11】
将硝酸铜6千克,硝酸锌8千克,硝酸铝2千克,硝酸银1千克和水100千克混合搅拌均匀得到金属盐溶液,将碳酸钠6千克和水110千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入1千克氧化铝,0.2千克石墨混合碾压,而后加入30重量%的水,造粒,300℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例12】
将硝酸铜60千克,硝酸锌10千克,硝酸铝10千克,硝酸铁0.01千克,氯化钯0.2千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例13】
将硝酸铜50千克,硝酸锌20千克,硝酸铝10千克,氯化铂0.2千克和水500千克混合搅拌均匀得到金属盐溶液,将碳酸钠30千克和水550千克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液混合均匀,在70℃反应1小时,将沉淀物洗涤干燥,而后加入6千克氧化铝,1千克石墨混合碾压,而后加入30重量%的水,造粒,270℃焙烧2小时,压片成型,得到样品组成见表1。
【实施例14】
将上述实施例制备的脱硫脱砷剂粉碎成20~40目的颗粒,将其填充到内径为1cm的反应器中,在常温、常压、体积空速为3000h-1的条件下,以含不同浓度硫、砷化合物杂质的氮气通过该反应器,对该脱硫脱砷剂进行评价,结果如表2所示。
【实施例15】
将上述实施例制备的脱硫脱砷剂粉碎成20~40目的颗粒,将其填充到内径为1cm的反应器中,在常温、常压、体积空速为3000h-1的条件下,以含不同浓度硫、砷化合物杂质的合成气通过该反应器,对该脱硫脱砷剂进行评价,结果如表3所示。
【实施例16】
将上述实施例制备的脱硫脱砷剂粉碎成20~40目的颗粒,将其填充到内径为1cm的反应器中,在常温、压力3.0MPa、质量空速为3.5h-1的条件下,以含不同浓度硫、砷化合物杂质的液态丙烯通过该反应器,对该脱硫脱砷剂进行评价,结果如表4所示。
表1
表2
表3
表4
Claims (9)
1.一种脱硫脱砷剂,以重量份数计,包括以下组分:
a)1~10份的绿铜锌矿;
b)10~50份的氧化铜;
c)10~60份的氧化锌;
d)0.01~1份的过渡金属Rh、Pt、Pd、Ag、Au中的至少一种。
2.根据权利要求1所述脱硫脱砷剂,其特征在于以脱硫脱砷剂重量份数计,绿铜锌矿含量为2~8份。
3.根据权利要求1所述脱硫脱砷剂,其特征在于以脱硫脱砷剂重量份数计,氧化铜含量为13~48份。
4.根据权利要求1所述脱硫脱砷剂,其特征在于以脱硫脱砷剂重量份数计,氧化锌含量为15~55份。
5.根据权利要求1所述脱硫脱砷剂,其特征在于以脱硫脱砷剂重量份数计,过渡金属的含量为0.1~0.5份。
6.根据权利要求1所述脱硫脱砷剂,其特征在于过渡金属为Rh或Ag的至少一种。
7.根据权利要求1所述脱硫脱砷剂,其特征在于脱硫脱砷剂的堆密度小于1.0kg/m3,侧压强度大于70N/粒。
8.权利要求1~5任一项所述的脱硫脱砷剂的制备方法,依次包括以下步骤:
(1)将硝酸铜、硝酸锌、硝酸铝、含有过渡金属M的水溶性无机盐和水按摩尔比计:Cu/Zn为0.1~2;Al/Zn为0~0.8且Al/Zn不为0;M/(Cu+Zn+Al)为0.001~0.1;(Cu+Zn+Al+M)/H2O为0.01~0.04的比例混合,搅拌均匀得溶液Ⅰ,其中,所述过渡金属M为Rh、Pt、Pd、Ag和Au中的至少一种;
(2)将碳酸钠、碳酸氢钠、碳酸铵中的至少一种和水按摩尔比为0.01~0.04的比例混合,搅拌均匀得溶液Ⅱ;
(3)将溶液Ⅰ和Ⅱ混合均匀,在40~90℃,反应0.5~3小时得沉淀物,将沉淀物洗涤干燥;
(4)将沉淀物、粘结剂、润滑剂混合碾压均匀,加入10~50重量%的水,造粒;
(5)将造粒好的粉料在170~300℃,焙烧1~5小时;
(6)压片成型为脱硫脱砷剂。
9.将权利要求1~7任一项所述的脱硫脱砷剂用于天然气、合成气、轻质气液态烃类的净化中。
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