Beta分子筛择形催化合成对二异丙苯的研究
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摘要
分子筛择形催化作为选择生成对位异构体的有效途径,一直以来都备受化工行业的重视,迄今已有很多科研人员投身这方面的研究。但作为芳烃烷基化的对位选择性催化剂,以ZSM系列、Y、MOR以及SAPO系列的研究居多,却鲜见有关β分子筛的报道。本论文主要针对β分子筛的改性和预处理方法,就异丙苯与异丙醇烷基化选择生成对二异丙苯的工艺,考察了影响对位选择性的各种因素,从而采取相应的措施来达到提高选择性的目的。实验过程中采用UV、XRD、FT-IR、NH_3-TPD、BET等手段对催化剂进行表征,并将其与催化性能进行关联。具体研究结果如下:
(1)在高压釜中进行反应时,异丙苯和异丙醇烷基化的适宜反应条件是:IPA/IPB=4:1(mol),催化剂用量10w%,反应温度250℃,反应时间5h,此时异丙苯的转化率达57.2%,二异丙苯异构体中的间对位比值m/p=1.21。
(2)综合对比ZSM-5、MOR、HY以及Hβ的物化性能,发现Hβ用作异丙苯异丙基化选择生成p-DIPB的分子筛催化剂,有效酸中心多,活性高,只是选择性有待进一步提高。
(3)分别对Hβ分子筛催化剂进行覆硅改性和杂元素氧化物改性。实验发现覆硅改性后,催化剂用量10w%,反应温度为250℃时,异丙苯转化率20%,选择性提高到m/p=1.00;铜、硼、磷氧化物改性后,相同的反应条件下,异丙苯转化率为70%,选择性不变或稍有下降;稀土金属元素氧化物(Ce_2O_3及La_2O_3)改性,在异丙苯转化率为30%时,产物中m/p=0.80,对位选择性大大提高。
(4)本论文在固定床微反装置上,考察扩散效应对异丙苯烷基化反应产物中异构体组成的影响。以样品4%Ceβ为前驱物,经表面覆碳预处理可获得高选择性的异丙苯烷基化催化剂,当反应条件为IPA/IPB=4:1、催化剂用量10mL、反应温度300℃、体积空速5h~(-1)、反应压力3MPa、氢气/反应原料=300(体积比)时,异丙苯转化率23%,产物组成m/p=0.66。
As an efficient way to produce p-isomers, shape-selective catalysts have been paid more and more attention by the chemical industry. Till now, lots of researchers dedicate to this field. ZSM series、Y、MOR and SAPO series are common p-selection zeolites to catalyze aromatics alkylation, but fewer records about zeoliteβ.
In this paper, the alkylation of cumene (IPB) with isopropyl alcohol (IPA) for preparing p-DIPB on modified Hβzeolites was studied. The purpose is to discuss the chief factors of p-DIPB selectivity, then corresponding measures can be advanced. The catalysts were characterized by means of UV、XRD、FT-IR、NH_3-TPD、BET etc., and these results were related to their catalytic performances. Some conclusions were obtained as below:
(1) When the alkylation of cumene with isopropyl alcohol proceeds in autoclave, the optimal reaction conditions are that, mole ratio of isopropyl alcohol to cumene 4:1, reaction temperature 250℃, catalyst dosage 10w%, and reaction time 5 hrs. Under this condition, a m/p=1.21 selective to m-DIPB/p-DIPB is achieved at a 57.2% cumene conversion.
(2) By comparison of the physical and chemical properties between ZSM-5、MOR、HY and Hβ, it was found, Hβis the most suitable choice for cumene isopropylation to generate p-DIPB in zeolite catalysts, for it has more effective acids with high activity. But its selectivity has to be further enhanced.
(3) When covered with silicone oxide, at 250℃, catalyst dosage 10w%, a m/p=1.00 selective is achieved at a 20% cumene conversion; and when loaded of copper、boron or phosphorus oxides, the cumene conversion increased to 70%, but the selectivity was unchanged or decreased. However, rare earth metal oxides (Ce_2O_3 and La_2O_3) modified zeolites had their conversion rate down to 30%, but the selectivity can improve to m/p=0.80.
(4) This paper studied the alkylation of cumene on fixed bed micro-reactor to discuss the effect of product diffusion. A highly selective catalyst for cumene alkylation is obtained by previous carbon-covering treatment to sample 4%Ceβ. When IPA/IPB=4:1, catalyst dosage 10mL, reaction temperature 300℃, WHSV 5h~(-1), reaction pressure 3MPa and H_2/materials=300 (volume ratio), a m/p=0.66 selective to m-DIPB/p-DIPB is achieved at a 23% cumene conversion.
(1)在高压釜中进行反应时,异丙苯和异丙醇烷基化的适宜反应条件是:IPA/IPB=4:1(mol),催化剂用量10w%,反应温度250℃,反应时间5h,此时异丙苯的转化率达57.2%,二异丙苯异构体中的间对位比值m/p=1.21。
(2)综合对比ZSM-5、MOR、HY以及Hβ的物化性能,发现Hβ用作异丙苯异丙基化选择生成p-DIPB的分子筛催化剂,有效酸中心多,活性高,只是选择性有待进一步提高。
(3)分别对Hβ分子筛催化剂进行覆硅改性和杂元素氧化物改性。实验发现覆硅改性后,催化剂用量10w%,反应温度为250℃时,异丙苯转化率20%,选择性提高到m/p=1.00;铜、硼、磷氧化物改性后,相同的反应条件下,异丙苯转化率为70%,选择性不变或稍有下降;稀土金属元素氧化物(Ce_2O_3及La_2O_3)改性,在异丙苯转化率为30%时,产物中m/p=0.80,对位选择性大大提高。
(4)本论文在固定床微反装置上,考察扩散效应对异丙苯烷基化反应产物中异构体组成的影响。以样品4%Ceβ为前驱物,经表面覆碳预处理可获得高选择性的异丙苯烷基化催化剂,当反应条件为IPA/IPB=4:1、催化剂用量10mL、反应温度300℃、体积空速5h~(-1)、反应压力3MPa、氢气/反应原料=300(体积比)时,异丙苯转化率23%,产物组成m/p=0.66。
As an efficient way to produce p-isomers, shape-selective catalysts have been paid more and more attention by the chemical industry. Till now, lots of researchers dedicate to this field. ZSM series、Y、MOR and SAPO series are common p-selection zeolites to catalyze aromatics alkylation, but fewer records about zeoliteβ.
In this paper, the alkylation of cumene (IPB) with isopropyl alcohol (IPA) for preparing p-DIPB on modified Hβzeolites was studied. The purpose is to discuss the chief factors of p-DIPB selectivity, then corresponding measures can be advanced. The catalysts were characterized by means of UV、XRD、FT-IR、NH_3-TPD、BET etc., and these results were related to their catalytic performances. Some conclusions were obtained as below:
(1) When the alkylation of cumene with isopropyl alcohol proceeds in autoclave, the optimal reaction conditions are that, mole ratio of isopropyl alcohol to cumene 4:1, reaction temperature 250℃, catalyst dosage 10w%, and reaction time 5 hrs. Under this condition, a m/p=1.21 selective to m-DIPB/p-DIPB is achieved at a 57.2% cumene conversion.
(2) By comparison of the physical and chemical properties between ZSM-5、MOR、HY and Hβ, it was found, Hβis the most suitable choice for cumene isopropylation to generate p-DIPB in zeolite catalysts, for it has more effective acids with high activity. But its selectivity has to be further enhanced.
(3) When covered with silicone oxide, at 250℃, catalyst dosage 10w%, a m/p=1.00 selective is achieved at a 20% cumene conversion; and when loaded of copper、boron or phosphorus oxides, the cumene conversion increased to 70%, but the selectivity was unchanged or decreased. However, rare earth metal oxides (Ce_2O_3 and La_2O_3) modified zeolites had their conversion rate down to 30%, but the selectivity can improve to m/p=0.80.
(4) This paper studied the alkylation of cumene on fixed bed micro-reactor to discuss the effect of product diffusion. A highly selective catalyst for cumene alkylation is obtained by previous carbon-covering treatment to sample 4%Ceβ. When IPA/IPB=4:1, catalyst dosage 10mL, reaction temperature 300℃, WHSV 5h~(-1), reaction pressure 3MPa and H_2/materials=300 (volume ratio), a m/p=0.66 selective to m-DIPB/p-DIPB is achieved at a 23% cumene conversion.
引文
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