CN105688986B - 一种用于改善烷基化反应催化活性的添加剂 - Google Patents
一种用于改善烷基化反应催化活性的添加剂 Download PDFInfo
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Abstract
本发明是一种改善烷基化反应催化活性的添加剂,具体说是在浓硫酸催化剂中加入微量的由烷基磷酸酯胺盐、蒎烯、烷基苯磺酸和重芳溶剂油组成的添加剂,催化异丁烷和烯烃的液相烷基化反应,在提高三甲基戊烷(包括2,2,4‑、2,3,3‑、2,3,4‑三甲基戊烷)等高辛烷值油类收率的同时,抑制副产物和高碳族烷烃的生成,可以提高烷基化油的品质;而其在浓硫酸催化剂体系中50ppm~500ppm时,能有效地增加异丁烷在硫酸相中的溶解度,提高烷基化进程,降低浓硫酸催化剂的损耗。
Description
技术领域
本发明属于浓硫酸催化剂技术领域,具体地说是一种用于改善烷基化反应催化活性的添加剂。
背景技术
随着中国经济的快速发展,汽车拥有量也逐渐攀升,随之而来的是汽车尾气对空气的污染也日趋严重,对于清洁汽油的需求量不断增加;由异丁烷和C4烯烃烷基化反应生成C8支链异辛烷产物,即烷基化汽油,是清洁环保的汽油高辛烷值调和组份,日益严格的燃料油标准的实施,对汽油中烯烃、芳烃、硫含量等进行了严格限制,烷基化油的重要性日显突出。
虽然国内外一直在研究开发固体酸烷基化技术,但工业化进程缓慢,其关键的技术难点在于经济有效地解决固体酸催化剂的失活和再生问题,目前已有Topsoe公司开发的FBA工艺采用二氧化硅负载液体酸催化剂,UOP公司开发的Alkylene工艺采用的Pt-KCL-AlCl3催化剂,ABB Lummus Global、Akzo Nobel、Fortum公司合作开发的AlkyClean工艺采用沸石催化剂,Rurgi公司基于反应蒸馏技术原理开发出的Eurofuel工艺采用沸石分子筛催化剂,美国Exelus公司开发的固体酸烷基化技术ExSact工艺及石油化工科学研究院开发的负载型杂多酸催化剂超临界烷基化工艺等取得了成果,并进行了中试或工业示范及工业化装置建设,但在经济性上仍然无法与传统的的浓硫酸和氢氟酸烷基化工艺相比。
在开发固体酸烷基化技术的同时,对于传统的液体酸烷基化技术的研究仍未停止,近年来取得进展的是液体酸添加助剂的开发,可以有效的降低液体酸的腐蚀性和酸耗,并提高产品的辛烷值和收率,如UOP和Texaco合作开发的Alkad工艺采用一种液体多氢络合物助剂,它可与HF形成多氢氟化物络合物,从而降低HF的损耗,并提高烷基化油的辛烷值,Phillips和Mobil公司联合推出了采用助剂降低HF挥发性的ReVAP工艺,俄罗斯专利(RU2114808C1)采用环丁砜和有机季铵盐作为浓硫酸催化剂的助剂,中国石油公司(台湾)采用2-萘磺酸作为助剂,美国专利(US3970721A)提出了采用三氟甲磺酸作为助剂,专利CN201110038062.8采用三氟乙醇或离子液体作为浓硫酸催化剂的助剂,专利CN104447160A采用磺酸酯和酸溶性油作为浓硫酸催化剂的助剂。
发明内容
本发明的目的是提供一种在硫酸法烷基化装置中用于改善烷基化反应催化活性的添加剂。
本发明的目的是通过如下技术方案来实现的:一种用于硫酸法烷基化反应中的添加剂,其特征在于,其特征在于,所述添加剂中的重量份数比为:烷基磷酸酯胺盐为1份;蒎烯为0.1~0.8份:烷基苯磺酸为0.1~0.4份:重芳溶剂油为0.1~0.8份。
本发明经优化的添加剂中的重量份数比为:烷基磷酸酯胺盐为1份;蒎烯为0.4~0.6份:烷基苯磺酸为0.3~0.4份:重芳溶剂油为0.5~0.7份。
本发明所述的添加剂,其添加量为浓硫酸重量的50ppm~500ppm。
本发明所述的烷基磷酸酯胺盐为C6~C12单烷基磷酸酯胺盐、二烷基磷酸酯胺盐或二者任意比例的混合。
本发明所述的烷基磷酸酯胺盐中的胺为含有C8~C24叔烷基伯胺。
本发明所述的蒎烯为α蒎烯、β蒎烯或二者任意比例的混合。
本发明所述的烷基苯磺酸为C8~C18烷基苯磺酸。
从上述可知,促进剂组成的发明包含三个活性成份,如单(或二)烷基磷酸酯胺盐、α(或β)蒎烯、C8~C20烷基苯磺酸。
本发明的促进剂可以有效地促进烷基化进程:
在硫酸法催化异丁烷和烯烃的烷基化反应中,异丁烷在硫酸相中的溶解度影响烷基化反应产物的选择性,添加剂中的表面活性成分降低了烃原料和浓硫酸催化剂之间的界面表面张力,从而增加机械搅拌或涡轮机在两相之间形成乳浊液的效率;氢化物转移催化剂,如蒎烯,增加了氢化物在酸催化剂和碳氢化合物之间的界面转移的速度。氢化物在整个界面的转移决定了在强酸催化剂下烷烃与烯烃烷基化的速度。添加剂可以提高进入酸沉降器的酸和烃乳化液的两相分离,通过防止酸以碎片的形式残留达到破乳效果,有助于降低酸消耗。
本发明提供的添加剂,用于硫酸法烷基化工艺中,在硫酸催化剂体系中加入微量的上述添加剂,能有效地增加异丁烷在硫酸相中的溶解度,提高三甲基戊烷(包括2,2,4-、2,3,3-、2,3,4-三甲基戊烷)等高辛烷值油类选择性,抑制副产物和高碳族烷烃的生成,可以提高烷基化油的品质,促进烷基化进程,降低浓硫酸催化剂的损耗。
本发明所说的添加剂的制备方法为:在烷基磷酸酯胺盐中加入蒎烯,搅拌30min,然后加入重芳溶剂油,继续搅拌30min,最后加入烷基苯磺酸,搅拌1h。
本发明添加剂评价利用500ml小型实验装置,反应器温度控制在8~12℃,压力在0.3~0.6MPa之间,进料烷烯比(v)8,在此条件下,对不同配比的添加剂进行评价。
本发明由于在异丁烷和烯烃在浓硫酸催化剂作用下进行烷基化反应,在浓硫酸催化剂体系中加入微量的含有单(或二)烷基磷酸酯胺盐、α(或β)蒎烯、C8~C20烷基苯磺酸和重芳溶剂油组份的促进剂可以提高三甲基戊烷(包括2,2,4-、2,3,3-、2,3,4-三甲基戊烷)等高辛烷值油类选择性,抑制副产物和高碳族烷烃的生成,可以提高烷基化油的品质,能有效地增加异丁烷在硫酸相中的溶解度,提高烷基化进程,降低浓硫酸催化剂的损耗。
下面将通过实施例对本发明做进一步说明,但下述的实例仅仅是本发明其中的例子而已,并不代表本发明所限定的权利范围,本发明权利范围以权利要求书为准。
具体实施方式:
实例1
按照添加剂的配制比例,保持蒎烯和烷基苯磺酸在添加剂中所占比例不变,调整烷基磷酸酯胺盐在添加剂中的比例,配制含烷基磷酸酯胺盐20%(T1)和40%(T2)两种添加剂,在微反评价装置上与不加添加剂的浓硫酸催化剂体系进行对比实验,结果见表1。
表1
浓H2SO4 | 浓H2SO4+T1 | 浓H2SO4+T2 | |
反应温度(℃) | 9 | 9 | 9 |
压力(MPa) | 0.5 | 0.5 | 0.5 |
烷烯比 | 8 | 8 | 8 |
烯烃转化率(%) | 100 | 100 | 100 |
产物组成(%) | |||
C5~7 | 11.58 | 8.13 | 7.21 |
C8(TMP) | 78.96(67.37) | 84.55(71.68) | 86.64(77.26) |
C9以上 | 9.46 | 7.32 | 6.15 |
实例2
按照添加剂的配制比例,保持烷基磷酸酯胺盐和蒎烯在添加剂中所占比例不变,调整烷基苯磺酸在添加剂中的比例,配制含烷基苯磺酸5%(T3)和10%(T4)两种添加剂,在微反评价装置上与不加添加剂的浓硫酸催化剂体系进行对比实验,结果见表2。
表2
浓H2SO4 | 浓H2SO4+T3 | 浓H2SO4+T4 | |
反应温度(℃) | 9 | 9 | 9 |
压力(MPa) | 0.5 | 0.5 | 0.5 |
烷烯比 | 8 | 8 | 8 |
烯烃转化率(%) | 100 | 100 | 100 |
产物组成(%) | |||
C5~7 | 11.58 | 9.39 | 8.56 |
C8(TMP) | 78.96(67.37) | 82.2(69.93) | 84.11(73.37) |
C9以上 | 9.46 | 8.41 | 7.33 |
实例3
按照添加剂的配制比例,保持烷基磷酸酯胺盐和烷基苯磺酸在添加剂中所占比例不变,调整蒎烯在添加剂中的比例,配制含蒎烯10%(T5)和30%(T6)两种添加剂,在微反评价装置上与不加添加剂的浓硫酸催化剂体系进行对比实验,结果见表3。
表3
浓H2SO4 | 浓H2SO4+T5 | 浓H2SO4+T6 | |
反应温度(℃) | 9 | 9 | 9 |
压力(MPa) | 0.5 | 0.5 | 0.5 |
烷烯比 | 8 | 8 | 8 |
烯烃转化率(%) | 100 | 100 | 100 |
产物组成(%) | |||
C5~7 | 11.58 | 9.12 | 8.78 |
C8(TMP) | 78.96(67.37) | 82.06(68.63) | 83.11(72.07) |
C9以上 | 9.46 | 8.82 | 8.11 |
实例4
按照添加剂的配制比例,保持蒎烯在添加剂中所占比例不变,调整蒎烯在添加剂中的比例,配制含烷基磷酸酯胺盐20%和烷基苯磺酸5%(T7)和含烷基磷酸酯胺盐40%和烷基苯磺酸含10%(T8)两种添加剂,在微反评价装置上与不加添加剂的浓硫酸催化剂体系进行对比实验,结果见表4。
浓H2SO4 | 浓H2SO4+T7 | 浓H2SO4+T8 | |
反应温度(℃) | 9 | 9 | 9 |
压力(MPa) | 0.5 | 0.5 | 0.5 |
烷烯比 | 8 | 8 | 8 |
烯烃转化率(%) | 100 | 100 | 100 |
产物组成(%) | |||
C5~7 | 11.58 | 10.06 | 6.03 |
C8(TMP) | 78.96(67.37) | 81.04(66.43) | 88.00(81.78) |
C9以上 | 9.46 | 8.9 | 5.97 |
实例5
按照添加剂的配制比例,保持烷基磷酸酯胺盐在添加剂中所占比例不变,调整蒎烯在添加剂中的比例,配制含蒎烯10%和烷基苯磺酸5%(T9)和含蒎烯30%和烷基苯磺酸含10%(T10)两种添加剂,在微反评价装置上与不加添加剂的浓硫酸催化剂体系进行对比实验,结果见表5
浓H2SO4 | 浓H2SO4+T9 | 浓H2SO4+T10 | |
反应温度(℃) | 9 | 9 | 9 |
压力(MPa) | 0.5 | 0.5 | 0.5 |
烷烯比 | 8 | 8 | 8 |
烯烃转化率(%) | 100 | 100 | 100 |
产物组成(%) | |||
C5~7 | 11.58 | 9.36 | 5.82 |
C8(TMP) | 78.96(67.37) | 82.6(70.83) | 88.27(82.11) |
C9以上 | 9.46 | 8.04 | 5.91 |
实例6
采用固定配比的添加剂,加入浓硫酸催化剂体系,加入量分别为100ppm(L1)和300ppm(L2),考察不同加剂量对浓硫酸催化烷基化反应的影响,结果见表6。
表6
浓H2SO4 | 浓H2SO4+L1 | 浓H2SO4+L2 | |
反应温度(℃) | 9 | 9 | 9 |
压力(MPa) | 0.5 | 0.5 | 0.5 |
烷烯比 | 8 | 8 | 8 |
烯烃转化率(%) | 100 | 100 | 100 |
产物组成(%) | |||
C5~7 | 11.58 | 7.34 | 5.79 |
C8(TMP) | 78.96(67.37) | 86.26(79.55) | 88.39(82.75) |
C9以上 | 9.46 | 6.40 | 5.82 |
从实例1、2、3、4、5中可以看出,在添加剂组分中,烷基磷酸酯胺盐、蒎烯、烷基苯磺酸的所占质量比提高,生成三甲基戊烷比例明显提高,副产物的生成得到有效抑制;从实例6中可以看出,加剂量大有助于三甲基戊烷的生成。
通过以上实例可以看出,加入添加剂后,烷基化反应的选择性明显调高,高辛烷值的烷基化油收率增加,副产物和高碳族烷烃的生产受到抑制;烷基磷酸酯胺盐在添加剂中的比例高有助于烷基化进程,蒎烯有助于抑制副产物的生成,烷基苯磺酸在添加剂中的比例不易过高,否则产品和浓硫酸分离时间长;加剂量增加,可以有助于促进烷基化进程,并降低浓硫酸的损耗。
Claims (3)
1.一种用于硫酸法烷基化反应中的添加剂,其特征在于,所述添加剂中的重量份数比为:烷基磷酸酯胺盐:蒎烯:烷基苯磺酸:重芳溶剂油为1份:(0.1~0.8)份:(0.1~0.4)份:(0.1~0.8)份;
所述的烷基磷酸酯胺盐为C6~C12单烷基磷酸酯胺盐、二烷基磷酸酯胺盐或二者任意比例的混合;
所述的烷基磷酸酯胺盐中的胺为含有C8~C24叔烷基伯胺;
所述的蒎烯为α蒎烯、β蒎烯或二者任意比例的混合;
所述的烷基苯磺酸为C8~C18烷基苯磺酸。
2.根据权利要求1所述的添加剂,其特征在于:所述添加剂中的重量份数比为:烷基磷酸酯胺盐:蒎烯:烷基苯磺酸:重芳溶剂油为1份:(0.4~0.6)份:(0.3~0.4)份:(0.5~0.7)份。
3.根据权利要求1所述的添加剂,其特征在于:所说的添加剂,其添加量为浓硫酸重量的50ppm~500ppm。
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CN102134507A (zh) * | 2011-02-15 | 2011-07-27 | 中国科学院过程工程研究所 | 以三氟乙醇或离子液体为助剂改性浓硫酸制备烷基化油的方法 |
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