CN1089272C - Adsorbent for preparing meta-xylene by adsorption and separation and its preparing process - Google Patents
Adsorbent for preparing meta-xylene by adsorption and separation and its preparing process Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 55
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 16
- 238000001179 sorption measurement Methods 0.000 title abstract description 40
- 238000000926 separation method Methods 0.000 title abstract description 10
- 239000010457 zeolite Substances 0.000 claims abstract description 56
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 55
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000440 bentonite Substances 0.000 claims description 8
- 229910000278 bentonite Inorganic materials 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 abstract description 41
- 239000002994 raw material Substances 0.000 abstract description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 13
- 239000008096 xylene Substances 0.000 abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 235000012216 bentonite Nutrition 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 159000000009 barium salts Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229940078552 o-xylene Drugs 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
一种以C8芳烃为原料经吸附分离制取间二甲苯的吸附剂及其制备方法。该吸附剂由35～81%的KY或BaY或KBaY型沸石、9～35%的ZSM-5型沸石和10～30%的粘结剂组成，具有较高的吸附容量，并对对二甲苯和乙苯有较高的吸附选择性。该吸附剂适用于含乙苯的混合二甲苯原料的吸附分离过程，能得到纯度＞99.9%的间二甲苯。An adsorbent for preparing m-xylene by adsorption and separation of C8 aromatic hydrocarbons as raw materials and a preparation method thereof. The adsorbent is composed of 35-81% KY or BaY or KBaY type zeolite, 9-35% ZSM-5 type zeolite and 10-30% binder. And ethylbenzene have higher adsorption selectivity. The adsorbent is suitable for the adsorption and separation process of mixed xylene raw materials containing ethylbenzene, and can obtain m-xylene with a purity >99.9%.
Description
本发明是一种吸附分离制取间二甲苯的吸附剂及其制备方法，更具体地说，是一种从含乙苯的混合二甲苯中吸附分离制取间二甲苯的吸附剂及其制备方法。The present invention is an adsorbent for absorbing and separating m-xylene and its preparation method, more specifically, an adsorbent for absorbing and separating m-xylene from mixed xylene containing ethylbenzene and its preparation method.
间二甲苯是二甲苯异构体中含量最多的组分，它既可以通过异构化反应生成对二甲苯、邻二甲苯，又可以直接氧化生成间苯二甲酸，作为改性聚酯和新型合成树脂的基本原料。间二甲苯的生产方法有：磺化法，HF-BF3抽提法，分子筛吸附分离法。其中，磺化法，HF-BF3抽提法易腐蚀设备，污染环境，正逐步被分子筛吸附分离法所代替。Meta-xylene is the component with the most content in xylene isomers. It can not only generate p-xylene and o-xylene through isomerization reaction, but also directly oxidize to generate isophthalic acid. It is used as a modified polyester and a new type of Basic raw material for synthetic resins. The production methods of m-xylene include: sulfonation method, HF-BF 3 extraction method, and molecular sieve adsorption separation method. Among them, sulfonation method and HF- BF3 extraction method are easy to corrode equipment and pollute the environment, and are gradually being replaced by molecular sieve adsorption separation method.
分子筛吸附分离法中使用的吸附剂有两类：一种是优先选择吸附混合二甲苯原料中间二甲苯的吸附剂，如USP4326092以NaY为吸附剂优先吸附间二甲苯，通过液相吸附分离模拟移动床工艺，制取纯度＞99.5％的间二甲苯。但是，采用此种方法设备要求复杂，操作精度要求极高。There are two types of adsorbents used in the molecular sieve adsorption separation method: one is the adsorbent that preferentially adsorbs the m-xylene of mixed xylene raw materials, such as USP4326092, which uses NaY as the adsorbent to preferentially adsorb m-xylene, and simulates the movement through liquid phase adsorption separation. bed process to produce m-xylene with a purity >99.5%. However, the equipment required by this method is complicated and the operation precision is extremely high.
另一种是优先选择吸附混合二甲苯原料中的乙苯及对二甲苯，从吸余相中得到间二甲苯的吸附剂，如CN1132192A以KY或KBaY分子筛为吸附活性组分，以膨润土为粘结剂制成吸附剂，通过气相吸附分离优先吸附对二甲苯，从吸余相得到纯度＞99.5％的间二甲苯。该技术操作简单，技术先进，工业装置运转良好。但是，该吸附剂对含有乙苯的原料，处理效果不好。CN1136549A则使用无粘结剂的Silicalite-1沸石吸附剂，优先吸附对二甲苯及乙苯，从吸余相得到纯度＞99.5％的间二甲苯。但是，Silicalite-1沸石的吸附容量低，使其应用范围受到很大的限制。The other is to preferentially select ethylbenzene and p-xylene in the mixed xylene raw material for adsorption, and obtain an adsorbent for m-xylene from the residual phase, such as CN1132192A, which uses KY or KBaY molecular sieves as the adsorption active component, and bentonite as the binding agent The adsorbent is prepared, and p-xylene is preferentially adsorbed by gas-phase adsorption separation, and m-xylene with a purity >99.5% is obtained from the absorption phase. The technology is simple to operate, advanced in technology, and the industrial device works well. However, this adsorbent has a poor treatment effect on raw materials containing ethylbenzene. CN1136549A uses binderless Silicalite-1 zeolite adsorbent to preferentially adsorb p-xylene and ethylbenzene, and obtain m-xylene with a purity >99.5% from the residual phase. However, the low adsorption capacity of Silicalite-1 zeolite greatly limits its application range.
本发明的目的是提供一种具有较高吸附容量的能从含乙苯的混合二甲苯中吸附分离高纯度间二甲苯的吸附剂及其制备方法。The purpose of the present invention is to provide a kind of adsorbent capable of adsorbing and separating high-purity m-xylene from mixed xylene containing ethylbenzene and its preparation method with higher adsorption capacity.
我们发现，以Y型沸石及ZSM-5型沸石为吸附活性组份，适当调节二者比例，充分利用Y型沸石吸附容量大而ZSM-5型沸石对乙苯(EB)和对二甲苯(PX)吸附选择性高的特点，将二者的优点结合起来，既能克服Y型沸石吸附剂对EB吸附选择性差的缺点，又能解决ZSM-5型沸石吸附剂吸附容量低的问题。We found that with Y-type zeolite and ZSM-5 type zeolite as adsorption active components, properly adjust the ratio of the two, make full use of the large adsorption capacity of Y-type zeolite and ZSM-5 type zeolite p-ethylbenzene (EB) and p-xylene ( PX) has the characteristics of high adsorption selectivity. Combining the advantages of the two can not only overcome the disadvantage of poor EB adsorption selectivity of Y-type zeolite adsorbent, but also solve the problem of low adsorption capacity of ZSM-5 zeolite adsorbent.
具体地说，本发明提供的吸附剂由Y型沸石、ZSM-5型沸石和粘结剂组成，其中各组份占吸附剂总重量的比例为：Y型沸石35～81％、ZSM-5型沸石9～35％、粘结剂10～30％。Specifically, the adsorbent provided by the present invention is composed of Y-type zeolite, ZSM-5 type zeolite and binder, wherein the ratio of each component to the total weight of the adsorbent is: Y-type zeolite 35-81%, ZSM-5 Type zeolite 9-35%, binder 10-30%.
所述的Y型沸石选自KY、BaY或KBaY。ZSM-5型沸石选自HZSM-5、NaZSM-5或全硅ZSM-5沸石(Silicalite-1)，但HZSM-5或NaZSM-5硅铝比应不小于20，且硅铝比越大越好，优选全硅ZSM-5沸石，即Silicalite-1。The Y-type zeolite is selected from KY, BaY or KBaY. ZSM-5 type zeolite is selected from HZSM-5, NaZSM-5 or all-silicon ZSM-5 zeolite (Silicalite-1), but the silicon-aluminum ratio of HZSM-5 or NaZSM-5 should not be less than 20, and the larger the silicon-aluminum ratio, the better , preferably all-silicon ZSM-5 zeolite, namely Silicalite-1.
所述粘结剂选自氧化铝、膨润土、高岭土、氧化硅或硅酸钠。优选氧化铝或膨润土。The binder is selected from alumina, bentonite, kaolin, silica or sodium silicate. Alumina or bentonite are preferred.
本发明所述吸附剂的制备方法为：将用K或Ba交换的Y型沸石或K-Ba交换的Y型沸石与ZSM-5型沸石以及粘结剂的前身物按照干基重量比35～81∶9～35∶10～30的比例混合后成型、干燥，并于300～600℃焙烧。The preparation method of the adsorbent of the present invention is: the Y-type zeolite exchanged with K or Ba or the Y-type zeolite exchanged by K-Ba and the precursor of the ZSM-5 type zeolite and the binder according to the dry weight ratio of 35 ~ The ratio of 81:9~35:10~30 is mixed, molded, dried, and fired at 300~600°C.
所述经交换的Y型沸石可用常规的方法制备，如，将NaY沸石用钾盐或钡盐进行交换，洗去阴离子后干燥，即得到KY或BaY沸石，也可先用钾盐交换，然后再用钡盐交换，制得KBaY沸石用于制备本发明吸附剂。所述用于离子交换的钾盐或钡盐选自K、Ba的可溶性盐，优选氯化钾、氯化钡、硝酸钡。The exchanged Y-type zeolite can be prepared by conventional methods, such as, NaY zeolite is exchanged with potassium salt or barium salt, washed off anions and then dried to obtain KY or BaY zeolite, which can also be exchanged with potassium salt first, and then Then exchange with barium salt to obtain KBaY zeolite for preparing the adsorbent of the present invention. The potassium salt or barium salt used for ion exchange is selected from soluble salts of K and Ba, preferably potassium chloride, barium chloride, and barium nitrate.
所述的ZSM-5型沸石选自硅铝比不小于20的NaZSM-5、HZSM-5或全硅ZSM-5沸石(Silicalite-1)，优选Silicalite-1沸石。The ZSM-5 zeolite is selected from NaZSM-5, HZSM-5 or all-silicon ZSM-5 zeolite (Silicalite-1) with a silicon-aluminum ratio of not less than 20, preferably Silicalite-1 zeolite.
所述粘结剂的前身物选自氢氧化铝、膨润土、高岭土、硅胶或水玻璃。优选氢氧化铝或膨润土。The precursor of the binder is selected from aluminum hydroxide, bentonite, kaolin, silica gel or water glass. Aluminum hydroxide or bentonite are preferred.
所述的成型方法为挤条或滚球成型，均采用常规的方法进行，即将Y型沸石、ZSM-5型沸石以及粘结剂的前身物按所需的比例混均后用水捏合，挤条成型，或者将原料混均后用水喷洒，边喷边滚成球形，然后干燥，并于300～600℃焙烧。也可用其他方法成型，如压片法。The molding method described is extruding or rolling ball molding, both of which are carried out by conventional methods, that is, Y-type zeolite, ZSM-5-type zeolite and the precursor of the binder are mixed according to the required ratio and then kneaded with water, extruded Forming, or mixing the raw materials and spraying with water, rolling into a ball while spraying, then drying, and roasting at 300-600°C. It can also be formed by other methods, such as tableting.
本发明提供的吸附剂适用于从含有乙苯的混合二甲苯中分离提纯高纯度间二甲苯的吸附分离过程。吸附剂的形状最好是条形或球形，也可以是其他形状，如颗粒状、片状。The adsorbent provided by the invention is suitable for the adsorption separation process of separating and purifying high-purity m-xylene from mixed xylene containing ethylbenzene. The shape of the adsorbent is preferably strip or spherical, and can also be in other shapes, such as granular and flake.
本发明吸附剂采用适当比例的Y型沸石和ZSM-5型沸石为活性组分，用简单的制备方法，使制得的吸附剂在具有高吸附容量的同时，又对PX和EB有良好的选择性。使用该吸附剂吸附分离含乙苯的混合二甲苯，可以在吸余相得到99.9％高纯度的间二甲苯(MX)。The adsorbent of the present invention adopts Y-type zeolite and ZSM-5 type zeolite in an appropriate proportion as active components, and uses a simple preparation method to make the obtained adsorbent have high adsorption capacity and good performance on PX and EB. selective. The adsorbent is used to adsorb and separate mixed xylenes containing ethylbenzene, and m-xylene (MX) with a high purity of 99.9% can be obtained in the absorption phase.
下面通过实例详细说明本发明，但本发明并不限于此。The present invention will be described in detail below by examples, but the present invention is not limited thereto.
实例中吸附剂的评价方法是：将原料加热至160～180℃，气相通过吸附剂床层，待达到吸附平衡后，用甲苯脱附出吸附剂吸附的物料，色谱分析其组成，计算出吸附容量。实例中CXY1代表吸附剂对混合二甲苯的饱和吸附容量，CPX+EB代表吸附剂对乙苯和对二甲苯的饱和吸附容量。The evaluation method of the adsorbent in the example is: heating the raw material to 160-180°C, the gas phase passes through the adsorbent bed, and after the adsorption equilibrium is reached, the adsorbent is desorbed with toluene, the composition is analyzed by chromatography, and the adsorption is calculated. capacity. In the example, C XY1 represents the saturated adsorption capacity of the adsorbent for mixed xylene, and C PX+EB represents the saturated adsorption capacity of the adsorbent for ethylbenzene and p-xylene.
实例1Example 1
本实例为本发明吸附剂的制备。This example is the preparation of the adsorbent of the present invention.
取52克(干基)NaY沸石分子筛(温州催化剂总厂生产)，用5重％的KCl溶液200毫升在90～100℃交换1小时，按此条件再重复交换4次，交换后的分子筛用去阳离子水洗涤至无游离氯离子后，在100℃烘干得到KY沸石。Get 52 grams (dry basis) of NaY zeolite molecular sieves (produced by Wenzhou Catalyst General Factory), exchange with 200 ml of 5% by weight KCl solution at 90-100° C. for 1 hour, repeat the exchange 4 times according to this condition, and use the molecular sieve after exchange with After washing with decationized water until free of free chloride ions, drying at 100°C to obtain KY zeolite.
将52克KY沸石、28克Silicalite-1沸石(上海染化七厂)与含干基氧化铝20克的氢氧化铝粉(齐鲁石化公司催化剂厂)混合均匀，加入适量水捏合后，挤成直径2毫米的条状物，100℃干燥，破碎成20～30目的颗粒，500℃培烧4小时，制得本发明吸附剂A。Mix 52 grams of KY zeolite, 28 grams of Silicalite-1 zeolite (Shanghai Dyestuff No. 7 Factory) and aluminum hydroxide powder (Qilu Petrochemical Company Catalyst Factory) containing 20 grams of dry basis alumina, and add appropriate amount of water to knead and extrude into Strips with a diameter of 2 mm were dried at 100°C, crushed into 20-30 mesh particles, and fired at 500°C for 4 hours to obtain the adsorbent A of the present invention.
实例2Example 2
取硅铝比为60的HZSM-5沸石35克(干基)和按实例1方法制得的KY沸石35克与30克膨润土混合均匀，再按实例1的方法挤条成型、干燥、破碎后经300℃培烧5小时制得本发明吸附剂B。Get the HZSM-5 zeolite 35 grams (dry base) that silicon-alumina ratio is 60 and KY zeolite 35 grams that make by the example 1 method mixes with 30 gram bentonites, press the method for example 1 again extrusion molding, after drying, crushing The adsorbent B of the present invention was prepared by calcination at 300°C for 5 hours.
实例3Example 3
取81克干基NaY沸石，按实例1的方法进行K交换，然后将K交换后的沸石用2重％的BaCl2溶液50毫升在90～100℃交换1小时，用去阳离子水洗涤至无游离氯离子，100℃烘干，得到KBaY沸石。Get 81 grams of dry base NaY zeolite, carry out K exchange by the method for example 1, then the zeolite after K exchange is used 2% by weight of BaCl2 solution 50 milliliters exchange 1 hour at 90～100 ℃, wash with deionized water until no Free chloride ions and dry at 100°C to obtain KBaY zeolite.
将81克上述制得的KBaY沸石与9克硅铝比为120的NaZSM-5沸石(干基)混合均匀后，再加入含10克干基氧化铝的氢氧化铝粉混均，按实例1的方法挤条成型、干燥、破碎后经500℃培烧4小时，制得本发明吸附剂C。After the NaZSM-5 zeolite (dry basis) that 81 grams of above-mentioned KBaY zeolites and 9 grams of silicon-aluminum ratios are 120 are mixed homogeneously, then add the aluminum hydroxide powder that contains 10 grams of dry basis aluminum oxides and mix homogeneously, press example 1 The method is extruded, dried and crushed, and then fired at 500°C for 4 hours to obtain the adsorbent C of the present invention.
对比例1Comparative example 1
取KBaY沸石80克与氢氧化铝粉20克(干基)混合均匀，挤条成型、干燥、破碎后，500℃培烧4小时，制得对比吸附剂E。Take 80 grams of KBaY zeolite and 20 grams of aluminum hydroxide powder (dry basis) and mix evenly, extrude, dry, crush, and burn at 500 ° C for 4 hours to prepare comparative adsorbent E.
对比例2Comparative example 2
取Silicalite-1沸石80克与氢氧化铝粉20克(干基)混合均匀，挤条成型、干燥、破碎后，500℃培烧4小时，制得对比吸附剂F。Take 80 grams of Silicalite-1 zeolite and 20 grams of aluminum hydroxide powder (dry basis), mix evenly, extrude, dry, crush, and then burn at 500 ° C for 4 hours to prepare comparative adsorbent F.
实例4Example 4
本实例对本发明吸附剂及对比吸附剂进行饱和吸附实验。In this example, saturated adsorption experiments were carried out on the adsorbent of the present invention and the comparative adsorbent.
将吸附剂填入80毫升吸附柱内，用N2吹扫，升温至170℃，通入含乙苯(EB)16.42％；对二甲苯(PX)17.69％；间二甲苯(MX)44.62％；邻二甲苯(OX)21.27％的原料，当吸附柱流出物中各组分浓度与原料相同时即达到吸附饱和。此时通入脱附剂甲苯进行脱附，同时收集脱附液进行色谱分析。计算得到的Cxy1及Cpx+EB分别列于表1。Fill the adsorbent into an 80 ml adsorption column, purging with N 2 , raising the temperature to 170°C, and introducing ethylbenzene (EB) 16.42%; p-xylene (PX) 17.69%; m-xylene (MX) 44.62% The raw material of o-xylene (OX) 21.27%, promptly reaches adsorption saturation when the concentration of each component in the adsorption column effluent is identical with the raw material. At this time, the desorbing agent toluene is introduced for desorption, and the desorbed liquid is collected for chromatographic analysis. The calculated C xy1 and C px+EB are listed in Table 1, respectively.
实例5Example 5
本实例以不同原料进行饱和吸附实验。In this example, saturated adsorption experiments were carried out with different raw materials.
将吸附剂C填入80毫升吸附柱内，用N2吹扫，升温至170℃，通入含EB20.58％；PX 20.65％；MX 58.77％的原料至吸附饱和，然后通入甲苯脱附，收集脱附液进行色谱分析，计算出的Cxy1＝15.03，Cpx+EB＝9.6。Fill the adsorbent C into an 80 ml adsorption column, purging with N 2 , raising the temperature to 170°C, passing through the raw material containing EB20.58%; PX 20.65%; MX 58.77% until the adsorption is saturated, and then passing through toluene for desorption , the desorbed liquid was collected for chromatographic analysis, and the calculated C xy1 =15.03, C px+EB =9.6.
实例6Example 6
本实例用本发明吸附剂进行吸附分离实验。This example uses the adsorbent of the present invention to carry out an adsorption separation experiment.
取70克吸附剂A填入吸附柱，用N2吹扫，升温至170℃，然后以2.3小时-1的重量空速通入吸附原料9.6克，原料组成同实例5。从吸余相中分离得到纯度为99.9％的间二甲苯(MX)3.5克。间二甲苯的纯度由色谱分析得到，下同。Get 70 grams of adsorbent A and fill it into the adsorption column, use N Purging , heat up to 170 ° C, then feed 9.6 grams of adsorption material at a weight space velocity of 2.3 hours −1 , the composition of the material is the same as in Example 5. 3.5 grams of m-xylene (MX) with a purity of 99.9% were separated from the absorption phase. The purity of m-xylene is obtained by chromatographic analysis, the same below.
实例7Example 7
取70克吸附剂B填入吸附柱，用N2吹扫，升温至180℃，然后以1.5小时-1的重量空速通入吸附原料9.6克，原料组成同实例5。从吸余相中分离得到纯度为99.9％的间二甲苯3.1克。Get 70 grams of adsorbent B and fill it into the adsorption column, use N Purging , heat up to 180 ° C, then feed 9.6 grams of adsorption material at a weight space velocity of 1.5 hours −1 , the composition of the material is the same as in Example 5. 3.1 g of m-xylene with a purity of 99.9% were separated from the absorption phase.
对比例3Comparative example 3
取70克对比例吸附剂F填入吸附柱，用N2吹扫，升温至180℃，然后以0.5小时-1的重量空速通入吸附原料9.6克，原料组成同实例5。从吸余相中分离得到纯度为99.9％的间二甲苯2.3克。Get 70 grams of comparative example adsorbent F and fill it into the adsorption column, use N Purging, heat up to 180 ° C, then feed 9.6 grams of adsorption raw material at a weight space velocity of 0.5 h -1 , the composition of the raw material is the same as in Example 5 . 2.3 g of m-xylene with a purity of 99.9% were separated from the absorption phase.
由实例6、7及对比例3可知，与对比吸附剂相比，本发明吸附剂可在较大的原料空速下，在吸余相得到较多的高纯度间二甲苯，说明本发明吸附剂对对二甲苯和乙苯具有较高的吸附选择性。From examples 6, 7 and comparative example 3, it can be seen that compared with the contrast adsorbent, the adsorbent of the present invention can obtain more high-purity m-xylene in the residual phase under a larger raw material space velocity, indicating that the adsorbent of the present invention The agent has high adsorption selectivity to p-xylene and ethylbenzene.
表1
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| CN102863048A (en) * | 2012-09-26 | 2013-01-09 | 中国科学院广州地球化学研究所 | Application of dealumination Y type zeolite in degrading organic pollutants in water under microwave induction |
| CN108264052B (en) * | 2017-01-03 | 2021-03-12 | 中国石油化工股份有限公司 | X/ZSM-5 core/shell molecular sieve and preparation method thereof |
| CN108262004B (en) * | 2017-01-03 | 2020-11-13 | 中国石油化工股份有限公司 | Para-xylene adsorbent and preparation method thereof |
| CN108262005B (en) * | 2017-01-03 | 2020-11-13 | 中国石油化工股份有限公司 | A kind of small ball adsorbent for adsorption and separation of p-xylene and preparation method thereof |
| CN108525650B (en) * | 2017-03-01 | 2020-11-13 | 中国石油化工股份有限公司 | X/Silicalite-1 core/shell molecular sieve and preparation method thereof |
| CN108525643B (en) * | 2017-03-01 | 2020-10-27 | 中国石油化工股份有限公司 | A kind of p-xylene adsorbent and preparation method thereof |
| CN108525641B (en) * | 2017-03-01 | 2020-11-13 | 中国石油化工股份有限公司 | Spherical adsorbent for adsorption and separation of p-xylene and preparation method thereof |
| CN111097371B (en) * | 2018-10-29 | 2022-03-11 | 中国石油化工股份有限公司 | Preparation method of paraxylene adsorbent |
| CN111138238B (en) * | 2020-01-03 | 2022-06-07 | 朱志荣 | Process method for producing m-xylene by mixing carbon octa-arene |
| CN113578258A (en) * | 2021-07-09 | 2021-11-02 | 山东亮剑环保新材料有限公司 | Spherical zeolite VOCs adsorbent with core-shell structure and preparation method thereof |
| CN113754543B (en) * | 2021-09-06 | 2022-09-20 | 南京工业大学 | Method for separating high-boiling-point isomer by utilizing gas phase adsorption of hierarchical pore silicon molecular sieve |
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