CN102616801A - Method for modification of zeolite NU-85 and aromatic isomerization catalyst containing modified zeolite NU-85 - Google Patents
Method for modification of zeolite NU-85 and aromatic isomerization catalyst containing modified zeolite NU-85 Download PDFInfo
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- CN102616801A CN102616801A CN2011100303392A CN201110030339A CN102616801A CN 102616801 A CN102616801 A CN 102616801A CN 2011100303392 A CN2011100303392 A CN 2011100303392A CN 201110030339 A CN201110030339 A CN 201110030339A CN 102616801 A CN102616801 A CN 102616801A
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Abstract
The invention discloses a method for modification of zeolite NU-85. The method comprises the following steps of treating Na-zeolite NU-85 by a silicon-containing compound in the presence of a gas phase medium, and then carrying out calcination in air, wherein the gas phase medium is selected from water vapor or nitrogen and the silicon-containing compound is selected from silica sol, silanes or siloxanes. The zeolite NU-85 modified by the method is loaded with a metal belonging to the VIII family thereby forming the aromatic isomerization catalyst used for a C8 aromatic isomerization reaction. The aromatic isomerization catalyst has a high isomerization activity and a high ethylbenzene conversion rate, reduces side reactions and greatly improves a C8 aromatic hydrocarbon yield.
Description
Technical field
The present invention is a kind of Zeolite modifying method and the arene isomerization catalyst that contains modified zeolite, specifically, is a kind of NU-85 Zeolite modifying method and the arene isomerization catalyst that contains this modified zeolite.
Background technology
P-Xylol (PX) and o-Xylol (OX) are important chemical material, are mainly used in to produce terephthalic acid, bis--terephthalate, Tetra hydro Phthalic anhydride, are applied to coating, dyestuff, agricultural chemicals and medicine and other fields in addition.Along with the development of these industries, the demand of PX and OX increases rapidly.At present, the Technology of raising the output PX and OX is mainly xylene isomerization, and this technology is that m-xylene and the ethylbenzene conversion that utility value is low is the important means of PX and OX.Through xylene isomerization reaction, p-Xylol reaches or near thermodynamic equilibrium value, ethylbenzene partly is converted into YLENE in the product, and side reaction product is non-aromatic hydrocarbons, also has a spot of benzene, toluene and C
9 +Heavy aromatics.Product is told PX and OX product through tripping device, again with the non-aromatic hydrocarbons of a spot of lightweight, benzene, toluene and C
9 +Heavy aromatics is separated, and leftover materials can be used as isomerized raw material recycle.
Generally speaking, C
8The used catalyzer of aromatics isomerization is a zeolite catalyst.These catalyzer of prior art are the catalyzer of basic components with the mordenite particularly, and general catalytic performance can only be provided, because the side reaction that they cause loss can not ignore.These side reactions comprise the open loop of naphthenic hydrocarbon, cracking then, or C
8The disproportionation of aromatic ring and transalkylation reaction, or aromatic hydrogenation reaction.Used with the catalyzer of ZSM-5 zeolite as basic components, it can use separately or with other zeolites, mix to use like mordenite, but best performance be not provided yet.
It is the catalyzer of basic components with EUO structure type zeolite that EP0923987A1 discloses a kind of.EUO structure type zeolite has the netted microvoid structure of one dimension, and its skeleton is the ten-ring duct of being made up of silica and aluminum-oxygen tetrahedron, and there is cage structure in the ovalize perforate in side, zeolite main aperture road.Because EUO type zeolite has particular structural, and to the good dispersivity of metal, physical strength is high, is that the catalyzer of acidity of catalyst constituent element shows good aromatics isomerization performance with EUO type zeolite.
CN200610170126.9 discloses the catalyzer of a kind of NES of containing structure type zeolite and EUO structure type zeolite, and EU-1 zeolite and NU-87 zeolite are mixed and made into carrier, loaded metal active ingredient again, and preferred platinum, this catalyzer is used for C
8Aromatics isomerization reacts, and can improve the transformation efficiency and the C of ethylbenzene
8The aromatic hydrocarbons net loss.
CN91104850.2 discloses NU-85 zeolite and compound method and application, and the NU-85 zeolite is the symbiosis crystal of EU-1 zeolite and NU-87 zeolite.The NU-85 zeolite is used for C
8A small amount of YLENE is only lost in the aromatics isomerization reaction, and the conversion of ethylbenzene when high temperature improves.
Summary of the invention
The purpose of this invention is to provide a kind of NU-85 Zeolite modifying method and be the C of active ingredient by modified zeolite
8Arene isomerization catalyst, described method of modifying can change the surface acidity of NU-85 zeolite, thereby improves the selectivity by the arene isomerization catalyst of modified zeolite preparation.
NU-85 Zeolite modifying method provided by the invention; Comprise sodium type NU-85 zeolite is handled with silicon-containing compound in the presence of gas phase media; Use air roasting then, described gas phase media is selected from water vapor or nitrogen, and silicon-containing compound is selected from silicon sol, silane or siloxanes.
The present invention carries out modification to the NU-85 zeolite with silicon-containing compound in the presence of gas phase media, make modification NU-85 zeolite through roasting, with the C of this modified zeolite preparation
8Arene isomerization catalyst has higher isomerization activity and conversion of ethylbenzene, and side reaction simultaneously reduces, C
8Aromatics yield significantly improves.
Embodiment
The present invention carried out for two steps with the NU-85 Si-Al zeolite and handles; The first step is handled with silicon-containing compound, and second step carried out roasting and makes modification NU-85 zeolite, and the surface acidity of this modified zeolite obtains modulation; Strength of acid descends; More help reducing the side reaction in the isomerization reaction, reduce the aromatic hydrocarbons rate of loss, thereby improve C
8Aromatics yield.Be mixed and made into carrier with sticker after modified zeolite processed Hydrogen; Perhaps directly modified zeolite and sticker are mixed and made into carrier; Carry out IX again and make sodium type modified zeolite be transformed into Hydrogen, in carrier, introduce VIII family metal again, promptly make isomerization catalyst after the roasting.
The inventive method is handled preferred 100～300 ℃ of the temperature of sodium type NU-85 zeolite with silicon-containing compound.Use silicon-containing compound to handle the silicon-dioxide that contains in the used silicon-containing compound of sodium type NU-85 zeolite and be 1～20%, preferred 1～10% of sodium type NU-85 zeolite quality.
The inventive method is injected in the gas phase media with silicon-containing compound processing NU-85 zeolite carries out, and when handling sodium type NU-85 zeolite with silicon-containing compound, gas phase media is 100～500 hours through the volume space velocity of sodium type NU-85 zeolite
-1, preferred 200～400 hours
-1Described gas phase media preferably water steam.The preferred silicon sol of described silicon-containing compound, preferred 10～30 quality % of the content of silicon-dioxide in the silicon sol.Handle preferred 2～12 hours of the time of sodium type NU-85 zeolite with silicon-containing compound.
After silicon-containing compound processing NU-85 zeolite, it is used air roasting, preferred 300～600 ℃, more preferably 400～500 ℃ of maturing temperatures, roasting time preferred 1～10 hour, more preferably 4～8 hours.
The modification NU-85 zeolite of the inventive method preparation is applicable to C
8The aromatics isomerization reaction with an amount of sticker moulding, can make arene isomerization catalyst with it.
Arene isomerization catalyst provided by the invention comprises modification NU-85 zeolite, the sticker of 39～94 quality % and the VIII family metal of 0.1～1.0 quality % by the inventive method preparation of 5～60 quality %, preferably includes modification NU-85 zeolite, the sticker of 54～89 quality % and the VIII family metal of 0.1～1.0 quality % by the inventive method preparation of 10～45 quality %.
Preferred silicon-dioxide of the sticker that contains in the above-mentioned catalyzer or aluminum oxide.Described VIII family metal is preferred platinum.
The existence form of modification NU-85 zeolite is preferably Hydrogen in the said catalyzer.The method for preparing Hydrogen modification NU-85 zeolite preferably adopts ion exchange method; Be about to na-pretreated zeolite and carry out IX with acid or ammonium salt solution; IX is preferably carried out under the condition of continuously stirring, preferred 60～100 ℃ of exchange temperature, preferred 0.5～4.0 hour of time.Gained solid drying, roasting promptly get h-type zeolite after will exchanging.Preferred 80～120 ℃ of described drying temperature, preferred 300～500 ℃ of maturing temperature.The preferred ammonium chloride of described ammonium salt, an ammonium nitrate, ammonium sulfate, volatile salt or bicarbonate of ammonia.The preferred hydrochloric acid of acid, nitric acid or the sulfuric acid that are used for IX.Gu liquid/mass ratio preferred 1～5 during IX: 1.
Above-mentioned Hydrogen modification NU-85 zeolite is mixed with sticker, preferably add extrusion aid and peptizing agent.The preferred sesbania powder of described extrusion aid, preferred rare nitric acid of peptizing agent or hydrochloric acid, its suitable concentration is 1～8 volume %.Said extrusion aid is preferably 0.5～5.0 quality % of solid material total amount, and the peptizing agent dosage is preferably 40～80 quality % of solid material total amount.The powder that adds extrusion aid and peptizing agent mixed pinch, extruded moulding, drying, roasting then, preferred 400～600 ℃ of maturing temperature, makes the carrier that contains Hydrogen modification NU-85 zeolite at preferred 2～8 hours of time.
The above-mentioned method for preparing carrier also can be mixed sodium type modification NU-85 zeolite earlier with sticker; Add extrusion aid and peptizing agent and mix the moulding of pinching bar; After drying, the roasting; Carry out IX with acid or ammonium salt solution again, the sodium type modification NU-85 zeolite in the carrier is converted into Hydrogen, used ion-exchange techniques is with the switching method of na-pretreated zeolite.
The described sticker of aforesaid method is selected from aluminum oxide, hydrated aluminum oxide, aluminium colloidal sol, silicon sol or silicon-aluminum sol, and preferred hydrated aluminum oxide is like pseudo-boehmite, boehmite.
After processing the carrier that contains Hydrogen modification NU-85 zeolite, preferably it is carried out hydrothermal treatment consists, preferred 300～600 ℃ of treatment temp, water vapor preferred 400～2000 hours to the volume space velocity of carrier
-1, preferred 2～20 hours of treatment time.
In carrier, introduce VIII family metal and preferably adopt pickling process, promptly use the solution impregnating carrier of the compound that contains VIII family metal, the catalyzer that the solid drying that will obtain after will flooding again, roasting promptly get oxidation state.Preferred 15～100 ℃ of described dipping temperature, preferred 2～50 hours of time, liquid/solid volume is than preferred 0.8～2.5 during dipping: 1.Preferred 80～120 ℃ of drying temperature behind the dipping, preferred 400～600 ℃ of maturing temperature, preferred 4～8 hours of time.
The described preferred platinum of compound of VIII family metal or nitrate salt, halogenide, ammonium complex compound, acetate, hydracid compound, hydracid ammonium salt, carbonyl compound or the oxy-compound of palladium of containing; Like platinum nitrate, Palladous nitrate, platinum chloride, Palladous chloride, Platinic chloride, the acid of chlorine palladium, ammonium palladic chloride, ammonium chloroplatinate, carbonyl halogenation palladium, carbonyl halogenation platinum, the acid of hexahydroxy-palladium or hexahydroxy-platinic acid, preferred Platinic chloride.
The oxidized catalyst of method for preparing need be reduced before use, and reductive condition is 0.1～5.0MPa, 250～600 ℃.The reducing gas that reduction is used can be hydrogen, carbon monoxide or methane, preferred hydrogen, preferred 0.5～6.0 hour of recovery time.
Arene isomerization catalyst provided by the invention is applicable to C
8The aromatics isomerization reaction; Suitable temperature of reaction is 300～500 ℃, preferred 350～430 ℃; The reaction total pressure is 0.4～2.0MPa, preferred 0.6～1.5MPa; Hydrogen dividing potential drop 0.5～1.5MPa, preferred 0.6～1.2MPa, hydrogen/hydrocarbon mol ratio is 1～8, preferred 3～6, charging mass space velocity 1～10, preferred 2～6.
Further specify the present invention through instance below, but the present invention is not limited to this.
The NU-85 zeolite that uses in instance and the Comparative Examples is synthetic by the CN91104850.2 disclosed method.
Instance 1
(1) preparation modification NU-85 zeolite
Get 50 gram sodium type NU-85 zeolites and place in the container, be heated to 180 ℃, feed water vapor, the volume space velocity that water vapor feeds is 300 hours
-1In water vapor, continue to add silicon sol (dioxide-containing silica 30 quality %) sodium type NU-85 zeolite is handled, the treatment time is 4 hours, and contained silicon-dioxide is 3.0% of zeolite quality in the silicon sol that adds in the treating processes.Zeolite is handled the back in container, changes blowing air, and with temperature rise to 450 ℃ of roastings 4 hours modified zeolite.After the cooling, carried out IX 2 hours in 90 ℃, wash to mother liquor and do not have cl ions with the aqueous ammonium chloride solution of 50 milliliter of 2 quality %, dry 4 hours Hydrogen modification NU-85 zeolite.
(2) preparation catalyzer
It is even with 30 gram aluminum oxide and 1 gram sesbania powder thorough mixing to get 20 gram Hydrogen modification NU-85 zeolite powders, and mixture of viscous form, extruded moulding are processed in the aqueous nitric acid stirring that adds 50 ml concns and be 3 quality %.With strip 120 ℃ of dryings 6 hours, pelletizing then, 550 ℃ of roastings 4 hours.In water vapour, handle then in 370 ℃ and handled 2 hours.Use again 50 ml concns be 3.36 mg/ml platinum acid chloride solution in 30 ℃ the dipping 24 hours; 120 ℃ of dryings 8 hours; 500 ℃ of roastings 4 hours in air again; Then under this temperature with hydrogen reducing 4 hours, make catalyzer C-2, wherein platiniferous 0.35 quality %, Hydrogen modification NU-85 zeolite 40 quality %, aluminum oxide 59.65 quality %.
Instance 2
Method by instance 1 prepares catalyzer; Different is (1) step sodium type NU-85 zeolite to be heated to 230 ℃; And then feed water vapor and silicon sol is handled, and use air roasting then, carry out again after ammonium exchange system gets Hydrogen modification NU-85 zeolite; Method according to (2) step prepares catalyzer, platiniferous 0.35 quality %, Hydrogen modification NU-85 zeolite 40 quality %, aluminum oxide 59.65 quality % among the catalyzer C-3 that makes.
Instance 3
Method by instance 1 prepares catalyzer; Different is that contained silicon-dioxide is 7.0% of zeolite quality in the silicon sol that in water vapor, adds in (1) step; Use air roasting then; Carry out again after ammonium exchange system gets Hydrogen modification NU-85 zeolite, prepare catalyzer, platiniferous 0.35 quality %, Hydrogen modification NU-85 zeolite 40 quality %, aluminum oxide 59.65 quality % among the catalyzer C-4 that makes according to the method in (2) step.
Comparative Examples 1
It is even with 30 gram aluminum oxide and 1 gram sesbania powder thorough mixing to get 20 gram sodium type NU-85 zeolite powders, and mixture of viscous form, extruded moulding are processed in the aqueous nitric acid stirring that adds 50 ml concns and be 3.0 quality %.With strip 120 ℃ of dryings 6 hours, pelletizing then, 550 ℃ of roastings 4 hours.Using 50 ml concns is that the aqueous ammonium chloride solution of 2.0 quality % carried out IX 2 hours in 90 ℃, washs to mother liquor and does not have cl ions.Using 50 ml concns again is the platinum acid chloride solution dipping 24 hours of 3.36 mg/ml; 120 ℃ of dryings 8 hours; Again in air in 500 ℃ of roastings 4 hours; Used hydrogen reducing again 4 hours, and processed catalyzer C-1, wherein platiniferous 0.35 quality %, Hydrogen NU-85 zeolite 40 quality %, aluminum oxide 59.65 quality %.
Instance 4～7
Following instance is estimated C
8The reactivity worth of arene isomerization catalyst.
At the stainless steel reactor of small stationary bed reaction device (filling 10 gram catalyzer among the φ 12mm * 800mm).With C
8Aroamtic hydrocarbon raw material is pumped into metering through surge tank.Reactant contacts with the catalyzer of heat and reacts, and product gets into the high pressure separating tank, and liquid product is told and measured with electronic scales by its bottom.Raw material and product are used HP 7890A gas chromatograph (FID, HP-wax chromatographic column) analysis respectively.Reaction conditions is: 370 ℃ of temperature, hydrogen dividing potential drop 0.6MPa, raw material charging mass space velocity 3.5h
-1, hydrogen/hydrocarbon mol ratio 4.5, used C
8The composition of aroamtic hydrocarbon raw material is seen table 1, and each instance catalyst system therefor numbering and reaction result are seen table 2.
In the reaction result shown in the table 2, the ratio (PX/X) and the conversion of ethylbenzene that account for YLENE with p-Xylol in the isomerization product are the catalyst activity index, with C
8Aromatics yield is the catalyst selectivity index.Can know by table 2 result, use modification NU-85 zeolite that the inventive method obtains obviously to be better than comparative catalyst C-1, especially C as the performance of catalyzer C-2, C-3 and the C-4 of active ingredient
8Aromatics yield significantly improves.
Table 1
Table 2
| Instance number | 4 | 5 | 6 | 7 |
| The catalyzer numbering | C-2 | C-3 | C-4 | C-1 |
| PX/X, quality % | 23.3 | 23.4 | 23.2 | 23.4 |
| Conversion of ethylbenzene, quality % | 31.7 | 31.9 | 31.3 | 30.5 |
| C 8Aromatics yield, quality % | 98.4 | 98.2 | 98.3 | 93.3 |
PX is a p-Xylol in the table, and X is a YLENE.
Claims (10)
1. a NU-85 Zeolite modifying method comprises sodium type NU-85 zeolite is handled with silicon-containing compound in the presence of gas phase media, and use air roasting then, described gas phase media is selected from water vapor or nitrogen, and silicon-containing compound is selected from silicon sol, silane or siloxanes.
2. according to the described method of claim 1, it is characterized in that the temperature of using silicon-containing compound to handle sodium type NU-85 zeolite is 100～300 ℃.
3. according to the described method of claim 1, it is characterized in that using silicon-containing compound to handle the silicon-dioxide that contains in the used silicon-containing compound of sodium type NU-85 zeolite and be 1～20% of sodium type NU-85 zeolite quality.
4. according to the described method of claim 1, when it is characterized in that with silicon-containing compound processing sodium type NU-85 zeolite, gas phase media is 100～500 hours-1 through the volume space velocity of sodium type NU-85 zeolite.
5. according to the described method of claim 1, after it is characterized in that handling sodium type NU-85 zeolite, it is 300～500 ℃ with the temperature of its roasting in air with silicon-containing compound.
6. arene isomerization catalyst comprises modification NU-85 zeolite, the sticker of 39～94 quality % and the VIII family metal of 0.1～1.0 quality % by the preparation of claim 1 method of 5～60 quality %.
7. according to the described catalyzer of claim 6, it is characterized in that described isomerization catalyst comprises modification NU-85 zeolite, the sticker of 54～89 quality % and the VIII family metal of 0.1～1.0 quality % by the preparation of claim 1 method of 10～45 quality %.
8. according to the described catalyzer of claim 6, it is characterized in that described sticker is silicon-dioxide or aluminum oxide.
9. according to the described catalyzer of claim 6, it is characterized in that described VIII family metal is a platinum.
10. according to the described catalyzer of claim 6, it is characterized in that described modification NU-85 zeolite is a Hydrogen.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104338551A (en) * | 2013-07-31 | 2015-02-11 | 中国石油化工股份有限公司 | Preparation method and application of xylene isomerization catalyst |
| CN108033456A (en) * | 2017-12-12 | 2018-05-15 | 国家地质实验测试中心 | A kind of modified zeolite for having the mesoporous clad structure of nano silicon dioxide and its preparation and application |
| CN110441458A (en) * | 2019-08-19 | 2019-11-12 | 山东绅联生物科技有限公司 | The gas chromatography analysis method of each substance in a kind of detection phthalic anhydride |
| CN110681414A (en) * | 2019-12-09 | 2020-01-14 | 山东国瓷功能材料股份有限公司 | Copper-containing loaded molecular sieve with high hydrothermal stability, and preparation method and application thereof |
| CN111115650A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Zeolite molecular sieve modification method |
| CN114425317A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst carrier, catalyst, preparation method and application thereof |
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| US6090272A (en) * | 1998-12-28 | 2000-07-18 | Phillips Petroleum Company | Process for converting a cracked gasoline using a zeolite-based catalyst material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104338551A (en) * | 2013-07-31 | 2015-02-11 | 中国石油化工股份有限公司 | Preparation method and application of xylene isomerization catalyst |
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| CN108033456A (en) * | 2017-12-12 | 2018-05-15 | 国家地质实验测试中心 | A kind of modified zeolite for having the mesoporous clad structure of nano silicon dioxide and its preparation and application |
| CN108033456B (en) * | 2017-12-12 | 2019-02-05 | 国家地质实验测试中心 | A kind of modified zeolite having the mesoporous clad structure of nano silica and its preparation and application |
| CN111115650A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Zeolite molecular sieve modification method |
| CN110441458A (en) * | 2019-08-19 | 2019-11-12 | 山东绅联生物科技有限公司 | The gas chromatography analysis method of each substance in a kind of detection phthalic anhydride |
| CN110681414A (en) * | 2019-12-09 | 2020-01-14 | 山东国瓷功能材料股份有限公司 | Copper-containing loaded molecular sieve with high hydrothermal stability, and preparation method and application thereof |
| CN114425317A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst carrier, catalyst, preparation method and application thereof |
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