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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- CN1089272C CN1089272C CN98102372A CN98102372A CN1089272C CN 1089272 C CN1089272 C CN 1089272C CN 98102372 A CN98102372 A CN 98102372A CN 98102372 A CN98102372 A CN 98102372A CN 1089272 C CN1089272 C CN 1089272C
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Abstract
The present invention relates to an adsorbent for preparing meta-xylene by adsorption and separation with C8 aromatic hydrocarbon as raw material and a preparing process thereof. The adsorbent is composed of 35 to 81% of KY zeolite or BaY zeolite or KBaY zeolite, 9 to 35% of ZSM-5 zeolite and 10 to 30% of adhesive. The adsorbent has the advantages of high adsorption capacity and high adsorption selectivity for meta-xylene and ethylbenzene. The adsorbent is suitable for adsorption and separation processes of mixed xylene raw material with the ethylbenzene; the meta-xylene of which the purity is larger than 99.9% is obtained.
Description
The present invention is sorbent material of a kind of preparing meta-xylene by adsorptive separation and preparation method thereof, more particularly, be a kind of from the xylol that contains ethylbenzene the sorbent material and preparation method thereof of preparing meta-xylene by adsorptive separation.
M-xylene is the maximum component of content in the xylene isomer, and it both can generate p-Xylol, o-Xylol by isomerization reaction, can direct oxidation generate m-phthalic acid again, as the basic raw material of modified poly ester and novel synthetic resins.The production method of m-xylene has: sulfonation method, HF-BF
3Extraction process, molecular sieve absorption process.Wherein, sulfonation method, HF-BF
3The extraction process corrosive equipment, contaminate environment is just progressively replaced by molecular sieve absorption process.
The sorbent material that uses in the molecular sieve absorption process has two classes: a kind of is the preferential sorbent material of selecting m-xylene in the absorption xylol raw material, as USP4326092 is sorbent material preferentially adsorbed m-xylene with NaY, by the liquid phase adsorption separation simulated moving bed technology, produce the m-xylene of purity＞99.5%.But, adopting this kind method equipment requirements complexity, performance accuracy requires high.
Another kind is preferential ethylbenzene and the p-Xylol of selecting in the absorption xylol raw material, from inhaling the sorbent material that Yu Xiangzhong obtains m-xylene, is the adsorption activity component as CN1132192A with KY or KBaY molecular sieve, with the wilkinite is that binding agent is made sorbent material, separate the preferentially adsorbed p-Xylol by Gas Phase Adsorption, from inhaling the surplus m-xylene that obtains purity＞99.5% mutually.This technological operation is simple, advanced technology, and full scale plant runs well.But this sorbent material is to containing the raw material of ethylbenzene, and treatment effect is bad.CN1136549A then uses the Silicalite-1 zeolite adsorbents of binder free, and preferentially adsorbed p-Xylol and ethylbenzene are from inhaling the surplus m-xylene that obtains purity＞99.5% mutually.But the loading capacity of Silicalite-1 zeolite is low, and its range of application is very restricted.
The purpose of this invention is to provide a kind of have than high-adsorption-capacity can be from the xylol that contains ethylbenzene the sorbent material and preparation method thereof of adsorption separation of high purity m-xylene.
We find, with y-type zeolite and ZSM-5 type zeolite is the adsorption activity component, suitably regulate the two ratio, make full use of the big and ZSM-5 type zeolite of y-type zeolite loading capacity to ethylbenzene (EB) and the high characteristics of p-Xylol (PX) adsorption selectivity, the advantages of the two is got up, the shortcoming of y-type zeolite sorbent material can be overcome, the low problem of ZSM-5 type zeolite adsorbents loading capacity can be solved again EB adsorption selectivity difference.
Specifically, sorbent material provided by the invention is made up of y-type zeolite, ZSM-5 type zeolite and binding agent, and wherein each component accounts for the ratio of sorbent material gross weight and is: y-type zeolite 35～81%, ZSM-5 type zeolite 9～35%, binding agent 10～30%.
Described y-type zeolite is selected from KY, BaY or KBaY.ZSM-5 type zeolite is selected from HZSM-5, NaZSM-5 or total silicon ZSM-5 zeolite (Silicalite-1), but HZSM-5 or NaZSM-5 silica alumina ratio should be not less than 20, and silica alumina ratio is the bigger the better preferred total silicon ZSM-5 zeolite, i.e. Silicalite-1.
Described binding agent is selected from aluminum oxide, wilkinite, kaolin, silicon oxide or water glass.Preferred aluminum oxide or wilkinite.
Preparation of adsorbent method of the present invention is: will be with the precursor of the y-type zeolite of the y-type zeolite of K or Ba exchange or K-Ba exchange and ZSM-5 type zeolite and binding agent according to butt weight ratio 35～81: 9～35: 10～30 mixed aftershaping, drying, and in 300～600 ℃ of roastings.
Described y-type zeolite through exchange can prepare with conventional method, as, the NaY zeolite is exchanged with sylvite or barium salt, flush away negatively charged ion after drying promptly obtains KY or BaY zeolite, also can exchange with sylvite earlier, and then, make the KBaY zeolite and be used to prepare sorbent material of the present invention with the barium salt exchange.The described sylvite of ion-exchange or the soluble salt that barium salt is selected from K, Ba of being used for, preferred Repone K, bariumchloride, nitrate of baryta.
Described ZSM-5 type zeolite is selected from silica alumina ratio and is not less than 20 NaZSM-5, HZSM-5 or total silicon ZSM-5 zeolite (Silicalite-1), preferred Silicalite-1 zeolite.
The precursor of described binding agent is selected from aluminium hydroxide, wilkinite, kaolin, silica gel or water glass.Preferred aluminium hydroxide or wilkinite.
Described forming method is extrusion or roller forming, all adopt conventional method to carry out, water was mediated after soon the precursor of y-type zeolite, ZSM-5 type zeolite and binding agent was mixed in required ratio, extruded moulding, the back water that perhaps raw material is mixed sprays, be rolled into sphere while spraying, dry then, and in 300～600 ℃ of roastings.Also available additive method moulding is as pressed disc method.
Sorbent material provided by the invention is applicable to the adsorption separation process that separates the purification high pureness meta-dimethyl benzene from the xylol that contains ethylbenzene.The shape of sorbent material is bar shaped or sphere preferably, also can be other shapes, as particulate state, sheet.
It is active ingredient that sorbent material of the present invention adopts the y-type zeolite and the ZSM-5 type zeolite of suitable proportion, uses simple preparation method, makes the sorbent material that makes when having high-adsorption-capacity, again PX and EB is had good selectivity.Use this adsorbents adsorb to separate the xylol that contains ethylbenzene, can inhale the surplus 99.9% highly purified m-xylene (MX) that obtains mutually.
Below by example in detail the present invention, but the present invention is not limited to this.
The evaluation method of sorbent material is in the example: raw material is heated to 160～180 ℃, and gas phase after waiting to reach adsorption equilibrium, goes out adsorbent material with the toluene desorption by adsorbent bed, and its composition of stratographic analysis calculates loading capacity.C in the example
XY1Represent the saturated adsorption capacity of sorbent material, C to xylol
PX+EBRepresent the saturated adsorption capacity of sorbent material to ethylbenzene and p-Xylol.
Example 1
This example is a preparation of adsorbent of the present invention.
Get 52 gram (butt) NaY zeolite molecular sieves (production of Wenzhou catalyzer head factory), with 200 milliliters of the KCl solution of 5 heavy % 90～100 ℃ of exchanges 1 hour, by this condition repeated exchanged 4 times again, molecular sieve after the exchange spends cationic water washing after do not have free chloro ion, obtains the KY zeolite 100 ℃ of oven dry.
52 gram KY zeolites, 28 gram Silicalite-1 zeolites (dying of Shanghai seven factories) are mixed with the aluminium hydrate powder (Qilu Petrochemical company catalyst plant) that contains butt aluminum oxide 20 grams, after adding the suitable quantity of water kneading, be extruded into the bar of 2 millimeters of diameters, 100 ℃ of dryings, be broken into 20～30 purpose particles, 500 ℃ of roasts 4 hours make adsorbent A of the present invention.
Example 2
Get silica alumina ratio and be 60 HZSM-5 zeolite 35 grams (butt) and mix with 30 gram wilkinites by KY zeolite 35 grams that example 1 method makes, again by the method extruded moulding of example 1, drying, fragmentation after 300 ℃ of roasts made adsorbent B of the present invention in 5 hours.
Example 3
Get 81 gram butt NaY zeolites, carry out the K exchange, then with the BaCl of the zeolite after the K exchange with 2 heavy % by the method for example 1
250 milliliters of solution spend the cationic water washing to there not being free chloro ion 90～100 ℃ of exchanges 1 hour, and 100 ℃ of oven dry obtain the KBaY zeolite.
It is after 120 NaZSM-5 zeolite (butt) mixes that the above-mentioned KBaY zeolites that make of 81 grams and 9 are restrained silica alumina ratios, adding the aluminium hydrate powder that contains 10 gram butt aluminum oxide again is mixed, press the method extruded moulding, drying, fragmentation of example 1 after 500 ℃ of roasts 4 hours make sorbent material C of the present invention.
Comparative Examples 1
Get KBaY zeolite 80 gram and mix with aluminium hydrate powder 20 grams (butt), after extruded moulding, drying, the fragmentation, 500 ℃ of roasts 4 hours make contrast sorbent material E.
Comparative Examples 2
Get Silicalite-1 zeolite 80 gram and mix with aluminium hydrate powder 20 grams (butt), after extruded moulding, drying, the fragmentation, 500 ℃ of roasts 4 hours make contrast sorbent material F.
Example 4
This example carries out saturated adsorption experiment to sorbent material of the present invention and contrast sorbent material.
Sorbent material is inserted in 80 milliliters of adsorption columns, used N
2Purge, be warming up to 170 ℃, feeding contains ethylbenzene (EB) 16.42%; P-Xylol (PX) 17.69%; M-xylene (MX) 44.62%; The raw material of o-Xylol (OX) 21.27%, it is saturated to reach absorption when each concentration of component is identical with raw material in the adsorption column effluent.Feed desorbing agent toluene and carry out desorption this moment, collects desorption liquid simultaneously and carry out stratographic analysis.The C that calculates
Xy1And C
Px+EBList in table 1 respectively.
Example 5
This example carries out saturated adsorption experiment with different material.
Sorbent material C is inserted in 80 milliliters of adsorption columns, use N
2Purge, be warming up to 170 ℃, feeding contains EB20.58%; PX 20.65%; The raw material of MX 58.77% is saturated to adsorbing, and feeds the toluene desorption then, collects desorption liquid and carries out stratographic analysis, the C that calculates
Xy1=15.03, C
Px+EB=9.6.
Example 6
This example carries out the fractionation by adsorption experiment with sorbent material of the present invention.
Get 70 gram adsorbent A and insert adsorption column, use N
2Purge, be warming up to 170 ℃, then with 2.3 hours
-1Weight space velocity feed absorption raw material 9.6 grams, raw material is formed with example 5.Surplusly separate that to obtain purity be 99.9% m-xylene (MX) 3.5 grams mutually from inhaling.The purity of m-xylene is obtained by stratographic analysis, down together.
Example 7
Get 70 gram adsorbent B and insert adsorption column, use N
2Purge, be warming up to 180 ℃, then with 1.5 hours
-1Weight space velocity feed absorption raw material 9.6 grams, raw material is formed with example 5.Surplusly separate that to obtain purity be 99.9% m-xylene 3.1 grams mutually from inhaling.
Comparative Examples 3
Get 70 gram Comparative Examples sorbent material F and insert adsorption column, use N
2Purge, be warming up to 180 ℃, then with 0.5 hour
-1Weight space velocity feed absorption raw material 9.6 grams, raw material is formed with example 5.Surplusly separate that to obtain purity be 99.9% m-xylene 2.3 grams mutually from inhaling.
By example 6,7 and Comparative Examples 3 as can be known, compare with the contrast sorbent material, sorbent material of the present invention can inhaling the surplus more high pureness meta-dimethyl benzene that obtains mutually, illustrate that sorbent material of the present invention has higher adsorption selectivity to p-Xylol and ethylbenzene under bigger raw material air speed.
Table 1
| Instance number | The sorbent material numbering | Adsorbent weight is formed | Saturated adsorption capacity, gram/100 grams | |||
| Y-type zeolite | ZSM-5 type zeolite | Binding agent | C XYI | C PX+EB | ||
| 1 | A | 52％KY | 28％Silicalite | 20％Al 2O 3 | 13.83 | 8.13 |
| 2 | B | 35％KY | 35％HZSM-5 | 30% wilkinite | 11.0 | 7.53 |
| 3 | C | 81％KBaY | 9％NaZSM-5 | 10％Al 2O 3 | 15.1 | 8.6 |
| Comparative Examples 1 | E | 80％KBaY | 20％Al 2O 3 | 15.00 | 7.32 | |
| Comparative Examples 2 | F | 80％Silicalite | 20％Al 2O 3 | 6.13 | 4.17 | |
Claims (9)
1, a kind of sorbent material of preparing meta-xylene by adsorptive separation is characterized in that this sorbent material is made up of 35～81% y-type zeolite, 9～35% ZSM-5 type zeolite and 10～30% binding agent.
2,, it is characterized in that described y-type zeolite is KY, BaY or KBaY according to the described sorbent material of claim 1.
3,, it is characterized in that described ZSM-5 type zeolite is that silica alumina ratio is not less than 20 ZSM-5 or total silicon ZSM-5 zeolite (Silicalite-1) according to the described sorbent material of claim 1.
4,, it is characterized in that described silica alumina ratio is not less than 20 ZSM-5 and is selected from NaZSM-5 or HZSM-5 according to the described sorbent material of claim 3.
5,, it is characterized in that described binding agent is selected from aluminum oxide, wilkinite, kaolin, silicon oxide or water glass according to the described sorbent material of claim 1.
6, the described preparation of adsorbent method of a kind of claim 1, it is characterized in that this method will be with the precursor of the y-type zeolite of K or Ba or K-Ba exchange and ZSM-5 type zeolite and binding agent according to butt weight ratio 35～81: 9～35: 10～30 mixed aftershaping, drying, and in 300～600 ℃ of roastings.
7, in accordance with the method for claim 6, it is characterized in that described ZSM-5 type zeolite is selected from silica alumina ratio and is not less than 20 NaZSM-5, HZSM-5 or total silicon ZSM-5 (Silicalite-1) zeolite.
8, in accordance with the method for claim 6, the precursor that it is characterized in that described binding agent is selected from aluminium hydroxide, wilkinite, kaolin, silica gel or water glass.
9, in accordance with the method for claim 6, it is characterized in that described forming method is extruded moulding or roller forming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102372A CN1089272C (en) | 1998-06-10 | 1998-06-10 | Adsorbent for preparing meta-xylene by adsorption and separation and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102372A CN1089272C (en) | 1998-06-10 | 1998-06-10 | Adsorbent for preparing meta-xylene by adsorption and separation and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1238238A CN1238238A (en) | 1999-12-15 |
| CN1089272C true CN1089272C (en) | 2002-08-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98102372A Expired - Lifetime CN1089272C (en) | 1998-06-10 | 1998-06-10 | Adsorbent for preparing meta-xylene by adsorption and separation and its preparing process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI491442B (en) * | 2009-08-17 | 2015-07-11 | China Petrochemical Technology Co Ltd | Adsorbent separation of m - xylene and its preparation |
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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 |
| CN108262004B (en) * | 2017-01-03 | 2020-11-13 | 中国石油化工股份有限公司 | Paraxylene adsorbent and preparation method thereof |
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| 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 |
| CN108525641B (en) * | 2017-03-01 | 2020-11-13 | 中国石油化工股份有限公司 | Small ball adsorbent for adsorbing and separating p-xylene and preparation method thereof |
| CN108525643B (en) * | 2017-03-01 | 2020-10-27 | 中国石油化工股份有限公司 | Paraxylene adsorbent 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5437129B1 (en) * | 1970-02-03 | 1979-11-13 | ||
| TW237422B (en) * | 1992-05-13 | 1995-01-01 | Licinvest Ag | |
| CN1132192A (en) * | 1995-03-30 | 1996-10-02 | 中国石油化工总公司石油化工科学研究院 | Technique for prepn. of high pureness meta-dimethyl benzene |
| CN1136549A (en) * | 1994-12-29 | 1996-11-27 | 中国石化金陵石油化工公司 | Method for separating m-xylene and ortho-xylene from mixed xylene and ethyl benzene |
-
1998
- 1998-06-10 CN CN98102372A patent/CN1089272C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5437129B1 (en) * | 1970-02-03 | 1979-11-13 | ||
| TW237422B (en) * | 1992-05-13 | 1995-01-01 | Licinvest Ag | |
| CN1136549A (en) * | 1994-12-29 | 1996-11-27 | 中国石化金陵石油化工公司 | Method for separating m-xylene and ortho-xylene from mixed xylene and ethyl benzene |
| CN1132192A (en) * | 1995-03-30 | 1996-10-02 | 中国石油化工总公司石油化工科学研究院 | Technique for prepn. of high pureness meta-dimethyl benzene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI491442B (en) * | 2009-08-17 | 2015-07-11 | China Petrochemical Technology Co Ltd | Adsorbent separation of m - xylene and its preparation |
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| CN1238238A (en) | 1999-12-15 |
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