CN101134171B - Method of producing C8 arene isomerization catalyst - Google Patents
Method of producing C8 arene isomerization catalyst Download PDFInfo
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Abstract
The process of preparing catalyst for C8 arene isomerization includes forming the mixture of EUO type molecular sieve and adhesive to obtain carrier, introducing VIII metal, drying, roasting and reducing with reductant gas. The catalyst contains EUO type molecular sieve in 5-90 wt%, adhesive 10-90 wt%, and VIII metal 0.1-5.0 wt%. The EUO type molecular sieve is prepared through mixing compound containing element X, compound containing element T, alkali metal compound and water, hydrothermal crystallization reaction in the presence of template agent precursor compounded with coarse dibromoalkane and monamine, collecting the solid and drying, where X is Si and Ge, T is Al, Fe, Ga or B, and the coarse dibromoalkane is mixture of dibromoalkane in the content of 80-95 wt%, Monobromoalkane and paraffin hydrocarbon diol. The catalyst has high ethyl benzene converting rate and low arene losing rate.
Description
Technical field
The present invention is a kind of C
8The preparation method of arene isomerization catalyst, specifically, be a kind of be the Preparation of catalysts method of acidity of catalyst constituent element with EUO type molecular sieve.
Background technology
The EUO structure molecular screen has the netted microcellular structure of one dimension, and its skeleton is the ten-ring duct of being made up of silica and aluminum-oxygen tetrahedron, the ovalize perforate, and orifice diameter is 0.41nm * 0.57nm.Have a cage structure in side, molecular sieve main aperture road, cage is 0.81nm deeply, and cage mouth diameter is 0.68nm * 0.58nm.Because EUO type molecular sieve has so special structure, and to the good dispersion of metal, the mechanical strength height is that the catalyst of acidity of catalyst constituent element shows good aromatics isomerization performance with EUO type molecular sieve.
US4537754 discloses a kind of EU-1 type molecular sieve and synthetic method thereof.Alkyl derivative or its precursor with polymethylene α-ω-diammonium ion are the template agent, after the even mixing of silicon source, aluminium source, alkali metal compound, template agent and water, make through hydrothermal crystallizing, described template agent precursor is parent diamines and alcohol or alkyl halide.Synthetic EU-1 type molecular sieve SiO
2/ Al
2O
3Mol ratio is 10～500.
US6514479 discloses a kind of particle diameter less than the aggregated particle size of 5 μ m and 90% EUO type molecular sieve and the synthetic method less than 200 μ m-40nm, and this method adopts ultrasonic wave to handle the size that reduces aggregated particle.The little molecular sieve of above-mentioned cohesive size has higher activity and conversion of ethylbenzene than common EUO type molecular sieve.EUO type molecular sieve employing polymethylene α-ω-diamines alkyl derivative or its precursor dibromo-hexane and trimethylamine are the template agent in this method, silicon source, aluminium source, alkali metal, template agent and selectable crystal seed are evenly mixed after behind the hydrothermal crystallizing, synthesize the Si-Al molecular sieve with EUO type structure.
US6342200 has reported that with polymethylene α-ω-diamines alkyl derivative be the template agent, the molecular sieve that is different from the EUO type by the adding structure is made crystal seed, with the mixture hydrothermal crystallizing that silicon source, aluminium source, alkali metal compound and template agent etc. form, the method for synthetic EUO type molecular sieve.
CN99127713.9 discloses a kind of method of the EUO of preparation type structural zeolite, this method adopts template agent precursor synthetic zeolite, its used precursor is monoamine and dihalo alkane or alkane diol, then adopting trimethylamine and dibromo-hexane in the example is template agent precursor preparation EUO type structural zeolite, can add crystal seed when synthetic, shorten the reaction time, but the reaction time when not adding crystal seed is longer, generally all above 100 hours.
US6723301 discloses the low EUO type molecular sieve of a kind of nitrogen content, this molecular sieve is the template agent with benzhydryl dimethyl amine and its derivative of low consumption, form in the homogeneous mixture system in silicon source, aluminium source, alkali metal compound, template agent and crystal seed, have a Si-Al molecular sieve that the Si/Al mol ratio is 7～26 EUO type structure through hydrothermal crystallizing is synthetic.
US6616910 is the template agent with benzhydryl dimethyl amine and its derivative, make crystal seed by adding EUO type molecular sieve, the reaction mixture that will be uniformly mixed to form by silicon source, aluminium source, alkali metal compound, template agent and crystal seed, through hydrothermal crystallizing, synthesize the Si/Al mol ratio and be 5～50 EUO type structure molecular screen.Be the C of acid constituent element preparation with Hydrogen EU-1 molecular sieve in this patent example
8Arene isomerization catalyst contains HEU-1 molecular sieve 10 quality %, aluminium oxide 89.7 quality %, and the Pt load capacity is 0.3 quality %, and HEU-1 molecular sieve Si/Al ratio is 26, Na in the molecular sieve
2O content counts 0.54% with the HEU-1 molecular sieve.Handle through reduction and presulfurization before the catalyst reaction, the mol ratio of surperficial sulphur/metal is 1.5.Under 390 ℃, the condition of reaction gross pressure 1.5MPa, hydrogen dividing potential drop 1.2MPa, carry out C
8The aromatics isomerization reaction, conversion of ethylbenzene is 40.1 quality %, and the aromatic hydrocarbons loss is 3.36 quality %, and paraxylene content is about 90.5 quality % of its thermodynamic equilibrium value in the product.
Above-mentioned prior art is described to have higher C
8In the catalyst of aromatics isomerization performance, active component EUO type molecular sieve all uses expensive template agent in preparation process, so the Catalyst Production cost is higher, and having limited with EUO type molecular sieve is the large-scale production and the application of acidity of catalyst constituent element.
Summary of the invention
The purpose of this invention is to provide a kind of C
8The preparation method of arene isomerization catalyst, the catalyst of this method preparation has good C
8The aromatics isomerization performance, and preparation cost is cheap.
C provided by the invention
8The preparation method of arene isomerization catalyst, comprise and to make carrier behind EUO type molecular sieve and the binding agent mixed-forming, in carrier, introduce VIII family metal again, drying, make catalyst with the reducibility gas reduction after the roasting, the EUO type molecular sieve that contains 5～90 quality % in the described catalyst, the VIII family metal of the binding agent of 10～90 quality % and 0.1～5.0 quality %, the preparation method of wherein said EUO type molecular sieve comprises and will contain the compound of element X, the compound of element T or contain the compound of element X and T simultaneously and alkali metal compound and water is mixed stirs, in the presence of the template agent precursor that thick two bromoalkanes and monoamine are made into, carry out the hydrothermal crystallizing reaction, dry behind the collection solid, described X is selected from silicon or germanium, T is selected from aluminium, iron, gallium or boron, described thick two bromoalkanes are two bromoalkanes, the mixture of the pure and mild alkane glycol of one bromo, wherein two bromoalkane content are 80～95 quality %.
Adopting thick dibromo-hexane and monoamine when the used EUO type molecular sieve of preparation catalyst is synthetic in the inventive method is template agent precursor, has not only enlarged the source of synthetic template used dose of molecular sieve, also makes the synthetic cost to reduce.The EUO type molecular sieve synthetic with this method is the catalyst that active component makes, and is used for C
8The aromatics isomerization reaction has higher paraxylene selectivity, and the aromatic hydrocarbons loss is lower, and conversion of ethylbenzene is higher.
Description of drawings
Fig. 1 is the x-ray diffraction spectra of catalyst activity component EUO type molecular sieve of the present invention.
The specific embodiment
The inventive method adopts the synthetic EUO type molecular sieve of a kind of template agent precursor of cheapness, and then with binding agent mixed carrier, in carrier, introduce VIII family metal component and promptly obtain catalyst.The template agent precursor that described synthetic EUO type molecular sieve uses is the mixture of thick two bromoalkanes and monoamine, described thick two bromoalkanes make after with alkane glycol bromination, wherein major part is two bromoalkanes, all the other are a unreacted alkane glycol and a bromhydrin, and these three kinds of materials all can generate the polymethylene diammonium ion and become the template agent with the monoamine reaction.Owing to thick two bromoalkanes are that raw material synthesizes with alkane glycol cheap and easy to get, its preparation is simple, and the synthetic crystallization time of EUO molecular sieve is shortened relatively, and the molecular sieve structure and the stable in properties of preparation.With the molecular sieve structure and the stable in properties of this method preparation, be used for C with the catalyst of its preparation
8Aromatics isomerization under the least possible situation of xylene loss, can make product amplitude peak ground form near thermodynamical equilibrium, and improve the conversion ratio of ethylbenzene.
Described thick two bromoalkanes are by the C of 0.5～10 quality %
4～C
8The C of alkane glycol, 8～20 quality %
4～C
8The C of pure and mild 80～90 quality % of a bromo
4～C
8Two bromoalkanes form, preferably form by the hexylene glycol of 0.5～10 quality %, the bromo hexanol of 8～20 quality % and the dibromo-hexane of 80～90 quality %.
Described thick two bromoalkanes adopt following method preparation: alkane two pure and mild hydrogen bromides in the presence of acidic catalyst, are fully reacted under reflux temperature, and then wash oil phase with aqueous slkali.The mol ratio of described hydrogen bromide and alkane glycol is 2～6: 1, and acidic catalyst is the concentrated sulfuric acid, the preferred sodium hydroxide solution of aqueous slkali, preferred 2～10 quality % of its concentration.
Described monoamine is that substituting group is C
1～C
3The tertiary amine of alkyl, preferred trimethylamine.
The ratio of the total mole number of each material that described monoamine and thick two bromoalkanes contain is 2.0～2.5: 1.
It is template agent precursor that the inventive method is selected thick two bromoalkanes and monoamine for use, described precursor is added in the reaction raw materials, under alkali condition, carry out the hydrothermal crystallizing reaction, template agent precursor generates the template agent in this course, and make reaction raw materials crystallization under the guide effect of template agent, generate the molecular sieve of desired structure.
In the inventive method, be selected from different compounds if contain the compound of X with the compound that contains T, then comparatively preferable methods is: the compound and the evenly mixed mixture that gets of suitable quantity of water that will contain element X earlier; To contain the compound of element T and suitable quantity of water again mixes and makes mixture; Two kinds of mixtures and template agent precursor of the present invention mixed make reactant mixture.
Each material in the mol ratio of oxide is in the described reactant mixture:
XO
2/T
2O
3 5～150
OH
-/XO
2 0.03～1.5
R/XO
2 0.02～0.7
M
2O/XO
2 0.015～0.8
H
2O/XO
2 1～300
The preferred mol ratio of each material is in the reactant mixture:
XO
2/T
2O
3 8～130
OH
-/XO
2 0.05～1.3
R/XO
2 0.08～0.6
M
2O/XO
2 0.025～0.65
H
2O/XO
2 5～250
Wherein, T
2O
3Expression is in the compound that contains aluminium, iron, gallium or boron of oxide, XO
2Expression is in the compound of the siliceous or germanium of oxide, and R is the total mole number of each material of containing of thick two bromoalkanes, and M is an alkali metal.Reactant mixture was 120～200 ℃ of hydrothermal crystallizings 6～350 hours, and crystallization is cooled to 15～30 ℃ rapidly with product after finishing, after filtration, obtain solid product after the washing.This product drying, roasting are promptly obtained EUO type molecular sieve.If not roasting can obtain moisture EUO type molecular sieve.Preferred 80～120 ℃ of described baking temperature, suitable sintering temperature is 500～600 ℃, preferred 6～30 hours of roasting time.
The preferred silica of described silicon-containing compound, silica gel, waterglass or esters of silicon acis, aluminum contained compound is sodium aluminate, aluminum sulfate, aluminum nitrate, alkoxy aluminum compound, aluminium oxide, alumine hydroxide colloid, boehmite or boehmite, the boron-containing compound preferred boric acid, contain the preferred gallium oxide of gallium compound, the preferred NaOH of alkali metal compound.
Can select the compound that contains element X and T simultaneously in the described method for use is the feedstock production molecular sieve, and preferably this kind compound is an amorphous silicon aluminium, and the mol ratio of its silica is 6～18, preferred 8～15.
The preferred Si-Al molecular sieve of EUO type molecular sieve of the inventive method preparation, its SiO
2/ Al
2O
3Mol ratio is 5～130, NH
3Adsorbance is 0.1～1.5 mM/gram.
The EUO type molecular sieve of the present invention's preparation is made carrier with binding agent mixing aftershaping, introduce VIII family metal again and promptly make catalyst in carrier, described catalyst need reduce before use, carries out Passivation Treatment again after the preferred reduction.
Described binding agent is selected from aluminium oxide, aluminium hydroxide, aluminium colloidal sol, Ludox or silicon-aluminum sol, and preferred aluminium hydroxide is as boehmite, boehmite.If binding agent is selected from the mixture of above-mentioned aluminum contained compound and silica, silica gel or silica-alumina gel, the content of silica, silica gel or silica-alumina gel is 5～75 quality % in the then described mixture.
In the shaping of catalyst process, preferably in molecular sieve and binding agent, add extrusion aid and peptizing agent.The preferred sesbania powder of described extrusion aid, preferred rare nitric acid of peptizing agent or hydrochloric acid, suitable concentration is 1～8 volume %.Described extrusion aid is preferably 0.5～9.0 quality % of solid material total amount, and peptizing agent is preferably 20～80 quality % of solid material total amount.
The EUO type molecular sieve that contains in the catalyst of the present invention's preparation is preferably Hydrogen.When described EUO type molecular sieve sodium type, preferably adopt ion-exchange to be converted into hydrogen type molecular sieve and prepare carrier with the binding agent mixed-forming again.Also sodium type EUO type molecular sieve can be mixed the first moulding in back with binding agent, change EUO type molecular sieve wherein into Hydrogen, the method preferred ion exchange process of transformation again.
With ion-exchange be: will carry out ion-exchange in molecular sieve or carrier immersion acid or the ammonium salt solution with the method that sodium type molecular sieve in sodium type molecular sieve or the carrier is converted into Hydrogen, ion-exchange is preferably carried out under the condition of continuous stirring, preferred 60～100 ℃ of exchange temperature, preferred 0.5～4.0 hour of time.Gained solid drying, roasting promptly get hydrogen type molecular sieve after will exchanging.Preferred 80～120 ℃ of described baking temperature, preferred 500～600 ℃ of sintering temperature, preferred 4～8 hours of roasting time.Described ion-exchange can be carried out repeatedly, and the sodium content in molecular sieve or carrier is 0.005～0.5 quality %.
The described preferred ammonium chloride of ammonium salt, ammonium nitrate, ammonium sulfate, ammonium carbonate or the carbonic hydroammonium that is used for ion-exchange, except that ammonium salt, also available ammoniacal liquor carries out ion-exchange.The described preferred hydrochloric acid of acid, nitric acid or the sulfuric acid that is used for ion-exchange.The NH that contains in the described exchange solution
4 +Or H
+Preferred 1～10 quality % of concentration.Gu liquid/mass ratio preferred 1～10 during ion-exchange: 1.
The preferred method of dipping that adopts is introduced carrier with VIII family metal in the inventive method.Be mixed with maceration extract with the compound that contains VIII family metal earlier during dipping, use the maceration extract impregnated carrier again, the solids drying that will obtain after will flooding then, roasting promptly obtain the catalyst of oxidation state.Preferred 15～100 ℃ of described dipping temperature, preferred 0.5～168 hour of time, liquid/solid volume is than preferred 0.8～2.5 during dipping: 1.Preferred 80～120 ℃ of described baking temperature, preferred 500～600 ℃ of sintering temperature, preferred 4～8 hours of time.
The described preferred platinum of compound of VIII family metal or nitrate, halide, ammonium complex compound, acetate, hydracid compound, hydracid ammonium salt, carbonyls or the hydroxy compounds of palladium of containing is as platinum nitrate, palladium nitrate, platinum chloride, palladium bichloride, chloroplatinic acid, the acid of chlorine palladium, ammonium chloropalladate, ammonium chloroplatinate, carbonyl halogenation palladium, carbonyl halogenation platinum, the acid of hexahydroxy palladium or hexahydroxy platinic acid.
Oxidized catalyst need be reduced before use, and reducing condition is normal pressure, 250～600 ℃.The preferred hydrogen of reducibility gas, carbon monoxide or methane that reduction is adopted, preferred 0.5～6.0 hour of time.
Catalyst after the reduction preferably carries out passivation before use, and the method for passivation is with the catalyst after the reducibility gas processing reduction that contains sulfide, carbide or ammonia, preferred 250～600 ℃ of passivation temperature, preferred 0.5～24 hour of passivation time.Preferred hydrogen sulfide of sulfide or sulfo-alkane that passivation is used, described carbide preferably vulcanizes carbide, C
4～C
7Alkane, C
4～C
7Alkene or C
6～C
9Aromatic hydrocarbons.The mol ratio of passivation rear catalyst surface sulphur, ammonia or carbon and surface metal element is 0.2～6.0.
The catalyst of method preparation provided by the invention is applicable to C
8The aromatics isomerization reaction, reaction temperature is 300～500 ℃, preferred 350～430 ℃, reaction gross pressure 0.4～2.0MPa, preferred 0.6～1.5MPa, the hydrogen dividing potential drop is 0.5～1.5MPa, preferred 0.6～1.2MPa, the charging mass space velocity is preferred 0.2～30 hour during reaction
-1, more preferably 1～10 hour
-1
Further specify the present invention below by example, but the present invention is not limited to this.
The X-ray diffraction of sample detects and is measured by Siemens D5005 type diffractometer in the example.Experiment condition is: x-ray source CuK α, and 0.154056 nanometer, 30 kilovolts of tube voltages, 20 milliamperes of tube currents, filter plate are Ni, sweep speed is 4 °/minute, 0.02 ° of step-length.
The relative crystallinity of sample: the ratio of each characteristic peak diffracted intensity sum in the XRD spectra of each characteristic peak diffracted intensity sum and standard specimen molecular sieve in the XRD spectra of tested molecular sieve.
The relative crystallinity of sample=(Ii/I) * 100%
Each characteristic peak diffracted intensity sum in the XRD spectra of the tested molecular sieve of Ii-in the formula,
Each characteristic peak diffracted intensity sum in the XRD spectra of I-standard specimen molecular sieve.
The NH of sample
3Adsorbance adopts the temperature programmed desorption method to measure.
Experimental technique: (1) with the roasting 4 hours in said apparatus in air, under 540 ℃, normal pressure of 200 milligrams of samples, reduces to 150 ℃ and continue to purge 1 hour with nitrogen then in nitrogen.(2) 150 ℃ feed NH
3Content is the nitrogen of 10 volume %, contacts 3 hours with sample, carries out NH
3Absorption.(3) feeding nitrogen purged 2 hours.When (4) carrying out temperature programming and take off, write down NH with thermal conductivity detector (TCD) with 5 ℃/minute heating rate
3Desorption peaks.According to NH
3The NH of desorption calculated by peak area sample
3Adsorbance.
Example 1～5
Following example prepares EUO type molecular sieve with the inventive method.
(1) preparation template agent precursor
Reflux condenser is being housed, agitator, in the four-hole boiling flask of thermometer and dropping funel, hexylene glycol (Beijing chemical reagents corporation that adds 100g earlier, chemical pure, content 〉=99 quality %) and the hydrogen bromide (Chemical Reagent Co., Ltd., Sinopharm Group of 75g, analyze pure, content 〉=99 quality %), 25 ℃ of stirrings, both are fully dissolved, be warming up to 40 ℃, slowly add the 100g concentrated sulfuric acid (Beijing Chemical Plant with dropping funel, chemical pure, 95～98 quality %), add the 200g hydrogen bromide again, slowly be warming up to reflux temperature reaction 4 hours, use isopyknic water respectively, the sodium hydroxide solution washing oil phase of 5 quality %, make it become neutral, obtain thick dibromo-hexane, wherein contain the dibromo-hexane of 85 quality %, the bromo hexanol of 13 quality % and the hexylene glycol of 2 quality %.The composition of described thick dibromo-hexane is all used the HP5890 chromatogram, Agilent DB-1 chromatogram column analysis.Analysis condition: 250 ℃ of injector temperatures, 300 ℃ of detector temperatures, 50～260 ℃ in post case, heating rate are 10 ℃/min.
Above-mentioned thick dibromo-hexane and trimethylamine solution (Beijing Jin Long chemical reagents corporation, 33 quality %) are made into template agent precursor N by 2.5: 1 the ratio of total mole number of each material in trimethylamine and the thick dibromo-hexane.
(2) preparation molecular sieve
(Wenzhou catalyst plant is produced with Ludox, dioxide-containing silica 29.2 quality %) and deionized water evenly be mixed and made into mixture, (Tianjin, Tianjin fine chemicals research institute of section produces with sodium aluminate again, alundum (Al content 45 quality %, sodium oxide content 33 quality %), NaOH and deionized water evenly are mixed and made into mixture.Be transferred in the autoclave after above-mentioned two mixtures and template agent N mixed, 180 ℃ left standstill crystallization 96 hours, were cooled to room temperature, and with the solid product that filters, obtains after the washing, 2 hours, 550 ℃ roastings of 110 ℃ of dryings obtained the EU-1 molecular sieve in 10 hours.Each example raw material consumption, molar ratio and synthetic EU-1 molecular sieve character see Table 1, and R is the total mole number of each material in the thick dibromo-hexane in the table 1, and wherein the X-ray diffraction pattern of the molecular sieve of example 1 preparation is seen Fig. 1.
Comparative Examples 1
Prepare the EUO molecular sieve according to USP6 514 479 methods.
Ludox and deionized water evenly are mixed and made into mixture; Sodium aluminate, NaOH and deionized water evenly are mixed and made into mixture; Mix above-mentioned two mixtures and template agent bromination 1,6-N, N, N, N ', N ', N '-hexamethyl hexamethylene diamine (production of Fluca company) is transferred in the autoclave after evenly, 180 ℃ left standstill crystallization 96 hours, be cooled to room temperature, after filtration, obtain solid product, 110 ℃ of dryings 2 hours after the washing, 550 ℃ of roastings obtained EUO type Si-Al molecular sieve D in 10 hours, and the raw material consumption in the preparation process, molar ratio and synthetic EU-1 molecular sieve character see Table 1.
Example 6
Following examples preparation C
8Arene isomerization catalyst.
(1) kneading and compacting: the molecular sieve D that gets 1 preparation of 45.00 gram examples
1, 45.94 grams the boehmite powder (Wenzhou catalyst plant is produced, Al
2O
3Content is 76.3 quality %), the dilute nitric acid solutions of 5 gram sesbania powder and 30 milliliter of 2 volume % mix, mix and make the bar shaped particle after pinching.
(2) ion-exchange: the aqueous ammonium chloride solution of getting the particle of 50 gram (1) step preparations and 250 milliliter of 5 quality % carried out ion-exchange 2 hours under 90 ℃, the condition of continuous stirring, exchange altogether 2 times.After the ion-exchange in the carrier sodium content be 0.04 quality %.110 ℃ of dryings 12 hours, 550 ℃ of roastings obtained carrier in 4 hours with the particle after the ion-exchange.
(3) carried metal element: get the carrier 30 as one kind gram that (2) step obtains after ion-exchange, 25 ℃ joined in the platinum acid chloride solution that 50 ml concns are 3.36 mg/ml dipping 36 hours, 110 ℃ of dryings 8 hours, and 580 ℃ of roastings 8 hours obtain oxidized catalyst E
1, it is formed and the platinum decentralization sees Table 2.
(4) reduction passivation: with the particle of step (3) preparation under 300 ℃, the condition of normal pressure, at H
2Handled 3 hours under the condition of flow velocity 100 ml/min, again with containing 30 quality %H
2The hydrogen treat of S 3 hours.The S/Pt mol ratio on passivation rear catalyst surface is 1.5.
Example 7
Get the EUO type molecular sieve of 33.50 gram examples, 2 preparations, 66.42 hydrated alumina (Beijing chemical reagent two factories of gram, content 65 quality %), the dilute nitric acid solutions of 5 gram silica gel (Shenyang Chemical Co., Ltd.'s productions), 40 milliliter of 3 volume % mix, and make the bar shaped particle after mixed the pinching.
Get 50 gram bar shaped particles and carry out dry after the ion-exchange, roasting by the method in 6 (2) steps of example and make carrier, sodium content is 0.045 quality % in the carrier.Method by (3) step prepares catalyst E
2, different is under 22 ℃ with carrier joined in the palladium nitrate solution that 65 ml concns are 4.38 mg/ml dipping 44 hours, the catalyst E that obtains after dry, the roasting
2Composition and platinum decentralization see Table 2.
With the particle of (3) step preparation under 400 ℃, the condition of normal pressure, with containing 50 volume %H
2Nitrogen, handled 4 hours with the flow velocity of 100 ml/min, again with containing 0.07 volume %CS
2Nitrogen treatment 24 hours.The S/Pa mol ratio on passivation rear catalyst surface is 1.8.
Example 8
Get the molecular sieve D of 45.00 gram examples, 3 preparations
3, 45.94 gram silica-alumina gels (Fushun catalyst plant, alumina content 67%, silica content 33 quality %), 5 gram sesbania powder, 35 milliliter of 2 volume % mixed in hydrochloric acid even, mix and make the bar shaped particle after pinching.
Get 50 gram bar shaped particles and carry out dry after the ion-exchange, roasting by the method in 6 (2) steps of example and make carrier, sodium content is 0.04 quality % in the carrier.Method by (3) step prepares catalyst E
3, different is carrier to be joined in the platinum acid chloride solution that 50 ml concns are 3.36 mg/ml flooded the catalyst E that obtains after drying, the roasting 36 hours
3Composition and platinum decentralization see Table 2.
Is the H of 40 ml/min with flow velocity with the particle of (3) step preparation under 350 ℃, the condition of normal pressure
2Handled 5 hours, and be cooled to 250 ℃, with containing 5.0 volume %NH
3N
2Handled 16 hours.The NH on passivation rear catalyst surface
3/ Pt mol ratio is 2.0.
Example 9
Molecular sieve D with 4 preparations of 9.50 gram examples
4, 90.40 gram boehmite powder, 5 gram sesbania powder, 30 milliliter of 4 volume % aqueous solution of nitric acid mix, mix and make the bar shaped particle after pinching.
Get 50 gram bar shaped particles and carried out ion-exchange 2 hours with the aqueous solution of nitric acid of 200 milliliter of 4 quality % under 80 ℃, the condition of continuous stirring, exchange altogether 2 times, sodium content is 0.052 quality % in the particle.110 ℃ of dryings 24 hours, 580 ℃ of roastings obtained carrier in 4 hours with this particle.
Get 30 gram carriers, joined in the platinum acid chloride solution that 29 ml concns are 5.21 mg/ml dipping 24 hours in 24 ℃, 110 ℃ of dryings 8 hours, 560 ℃ of roastings 8 hours, the catalyst E that obtains
4Composition and platinum decentralization see Table 2.
With catalyst E
4Under 350 ℃, normal pressure, be the H of 60 ml/min in flow velocity
2In reduce and handled 5 hours, be 1 hour at 450 ℃, 1.5MPa, charging mass space velocity again
-1Condition under, use C
8Aromatic hydrocarbons (consisting of meta-xylene 67.08 quality %, ortho-xylene 24.31 quality %, ethylbenzene 8.60 quality %) was handled 2 hours.The C/Pt mol ratio on passivation rear catalyst surface is 1.3.
Example 10
(1) ion-exchange: the EUO type molecular sieve D that gets 5 preparations of 20 gram examples
5Under 90 ℃, continuous stirring, carried out ion-exchange 2 hours with the aqueous ammonium chloride solution of 200 milliliter of 4 quality %, exchange altogether 2 times.Fully sodium content is 0.02 quality % in the molecular sieve of washing back, and the molecular sieve after the ion-exchange was made hydrogen type molecular sieve in 12 hours 110 ℃ of dryings.
(2) kneading and compacting: the aqueous solution of nitric acid of 5.6 gram hydrogen type molecular sieves, 59.2 gram boehmites, 5 gram sesbania powder, 30 milliliter of 4 volume % is mixed, make the bar shaped particle after mixed the pinching, 540 ℃ of roastings made carrier in 6 hours.
(3) carried metal element: get carrier granular 30 grams of (2) step preparation, and joined in the platinum acid chloride solution that 50 ml concns are 3.36 mg/ml dipping 36 hours, 110 ℃ of dryings 8 hours, 580 ℃ of roastings 8 hours, the catalyst E that makes at 25 ℃
5Composition and platinum decentralization see Table 2.
(4) reduction: will (3) particle of step preparation under 400 ℃, normal pressure, the H of usefulness flow velocity 60 ml/min
2Reduced 5 hours.
Comparative Examples 2
Method by example 6 prepares comparative catalyst E, and different is that the EUO type molecular sieve that adopts is the molecular sieve D of Comparative Examples 1 preparation, and composition and the platinum decentralization of the catalyst E that obtains after the roasting see Table 2, and passivation rear catalyst surface S/Pt mol ratio is 1.5.
Example 11～16
Below to the C of the catalyst of the inventive method preparation
8The aromatics isomerization performance is estimated.
The stainless steel reactor of the small-sized reaction unit of continuous-flow fixed bed (80mm *
Filling 10 gram catalyst 20mm).With C
8Aromatic hydrocarbons is pumped into reactor through surge tank with metering and contacts with hot catalyst and react, and product enters the high pressure knockout drum, and liquid product is told and measured with electronic scale bottom it.Raw material and product are used HP 4890-II gas chromatograph (TCD, Al respectively
2O
3-PLOT chromatographic column) analyzes.Described C
8Aromatic hydrocarbons consists of meta-xylene 67.08 quality %, ortho-xylene 24.31 quality %, ethylbenzene 8.60 quality %, each example catalyst system therefor and reaction condition and the results are shown in Table 3.
Table 3 is the result show, the catalyst of the inventive method preparation is used for C
8The aromatics isomerization reaction is compared with the comparative catalyst, and conversion of ethylbenzene is high slightly, and the aromatic hydrocarbons loss late is less, but the preparation cost of used molecular sieve greatly reduces.
Table 1
*HxBr
2Be 1,6-N, N, N, N ', N ', N '-hexamethyl hexamethylene diamine, skeleton symbol are [Me
3N (CH
2)
6NMe
3 2+(Br
-)
2]
Table 2
Table 3
Claims (20)
1. C
8The preparation method of arene isomerization catalyst, comprise and to make carrier behind EUO type molecular sieve and the binding agent mixed-forming, in carrier, introduce VIII family metal again, drying, make catalyst with the reducibility gas reduction after the roasting, the EUO type molecular sieve that contains 5～90 quality % in the described catalyst, the VIII family metal of the binding agent of 10～90 quality % and 0.1～5.0 quality %, described each constituent content sum is 100%, the preparation method of wherein said EUO type molecular sieve comprises and will contain the compound of element X, the compound of element T or contain the compound of element X and T simultaneously and alkali metal compound and water is mixed stirs, in the presence of the template agent precursor that thick two bromoalkanes and monoamine are made into, carry out the hydrothermal crystallizing reaction, dry behind the collection solid, described X is selected from silicon or germanium, T is selected from aluminium, iron, gallium or boron, described thick two bromoalkanes are two bromoalkanes, the mixture of the pure and mild alkane glycol of one bromo, wherein two bromoalkane content are 80～95 quality %, described thick two bromoalkanes adopt the preparation of following method: with alkane two pure and mild hydrogen bromides in the presence of acidic catalyst, under reflux temperature, fully react, and then wash oil phase with aqueous slkali.
2. according to the described preparation method of claim 1, it is characterized in that the C of described thick two bromoalkanes by 0.5～10 quality %
4～C
8The C of alkane glycol, 8～20 quality %
4～C
8The C of pure and mild 80～90 quality % of a bromo
4～C
8Two bromoalkanes form, described each constituent content sum is 100%.
3. according to the described preparation method of claim 1, it is characterized in that described thick two bromoalkanes are made up of the hexylene glycol of 0.5～10 quality %, the bromo hexanol of 8～20 quality % and the dibromo-hexane of 80～90 quality %, described each constituent content sum is 100%.
4. in accordance with the method for claim 1, the mol ratio that it is characterized in that described hydrogen bromide and alkane glycol is 2～6: 1, and acidic catalyst is the concentrated sulfuric acid, and aqueous slkali is a sodium hydroxide solution.
5. in accordance with the method for claim 1, it is characterized in that described monoamine is that substituting group is C
1～C
3The tertiary amine of alkyl.
6. in accordance with the method for claim 5, it is characterized in that described monoamine is a trimethylamine.
7. in accordance with the method for claim 1, the ratio that it is characterized in that the total mole number of each material that described monoamine and thick two bromoalkanes contain is 2.0～2.5: 1.
8. in accordance with the method for claim 1, it is characterized in that among the preparation method of described EUO type molecular sieve, each material in the mol ratio of oxide is in the reactant mixture:
XO
2/T
2O
3 5～150
OH
-/XO
2 0.03～1.5
R/XO
2 0.02～0.7
M
2O/XO
2 0.015～0.8
H
2O/XO
2 1～300
Wherein, R is the total mole number of each material of containing of thick two bromoalkanes, and M is an alkali metal, and reactant mixture was 120～200 ℃ of hydrothermal crystallizings 6～350 hours.
9. in accordance with the method for claim 8, it is characterized in that each material in the described reactant mixture in the mol ratio of oxide is:
XO
2/T
2O
3 8～130
OH
-/XO
2 0.05～1.3
R/XO
2 0.08～0.6
M
2O/XO
2 0.025～0.65
H
2O/XO
2 5～250
10. in accordance with the method for claim 1, it is characterized in that described silicon-containing compound is silica, silica gel, waterglass or esters of silicon acis, aluminum contained compound is sodium aluminate, aluminum sulfate, aluminum nitrate, alkoxy aluminum compound, aluminium oxide, alumine hydroxide colloid, boehmite or boehmite.
11. in accordance with the method for claim 1, it is characterized in that the described compound that contains element X and T is an amorphous silicon aluminium, described boron-containing compound is a boric acid, and containing gallium compound is gallium oxide, and alkali metal compound is a NaOH.
12. in accordance with the method for claim 1, it is characterized in that described EUO type molecular sieve is an EUO type Si-Al molecular sieve, described binding agent is selected from aluminium oxide, silica gel or silica-alumina gel, or the mixture of aluminium oxide and silica, silica gel or silica-alumina gel.
13. it is characterized in that in accordance with the method for claim 12, the content of silica, silica gel or silica-alumina gel in the described mixture is 5～75 quality %.
14. in accordance with the method for claim 1, it is characterized in that described EUO type molecular sieve is a Hydrogen.
15. in accordance with the method for claim 1, when it is characterized in that described EUO type molecular sieve is the sodium type, adopt ion-exchange to be converted into hydrogen type molecular sieve and carry out moulding again, or with EUO type molecular sieve mix with binding agent the back first moulding, change EUO type molecular sieve into Hydrogen with ion-exchange again.
16. in accordance with the method for claim 1, it is characterized in that introducing VIII family metal with the compound solution impregnated carrier that contains VIII family metal makes catalyst.
17. in accordance with the method for claim 16, it is characterized in that containing nitrate, halide, ammonium complex compound, acetate, hydracid compound, hydracid ammonium salt, carbonyls or the hydroxy compounds that VIII family metallic compound is selected from platinum or palladium.
18. in accordance with the method for claim 1, it is characterized in that the catalyst after the reduction is carried out passivation with the reducibility gas that contains sulfide, carbide or ammonia 250～600 ℃ of processing.
19. according to the described preparation method of claim 18, it is characterized in that described sulfide is hydrogen sulfide or sulfo-alkane, described carbide is sulfuration carbide, C
4～C
7Alkane, C
4～C
7Alkene or C
6～C
9Aromatic hydrocarbons.
20. it is characterized in that in accordance with the method for claim 18, the mol ratio of Passivation Treatment rear catalyst surface sulphur, ammonia or carbon and surface metal element is 0.2～6.0.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4537754A (en) * | 1980-06-12 | 1985-08-27 | Imperial Chemical Industries Plc | Zeolite EU-1 and a method of making zeolite EU-1 |
| CN1259399A (en) * | 1998-11-02 | 2000-07-12 | 法国石油公司 | Method for preparing EUO type structural zeolite and its use as catalyst |
| CN1260239A (en) * | 1998-11-02 | 2000-07-19 | 法国石油公司 | Method for preparing EUO structural zeolite and use thereof as catalyst |
| US6514479B1 (en) * | 1998-12-23 | 2003-02-04 | Institut Francais Du Petrole | EUO zeolite comprising crystals and aggregates of crystals with specific granulometrys and its use as a catalyst in the isomerisation of C8 aromatic compounds |
-
2006
- 2006-08-31 CN CN2006101127359A patent/CN101134171B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4537754A (en) * | 1980-06-12 | 1985-08-27 | Imperial Chemical Industries Plc | Zeolite EU-1 and a method of making zeolite EU-1 |
| CN1259399A (en) * | 1998-11-02 | 2000-07-12 | 法国石油公司 | Method for preparing EUO type structural zeolite and its use as catalyst |
| CN1260239A (en) * | 1998-11-02 | 2000-07-19 | 法国石油公司 | Method for preparing EUO structural zeolite and use thereof as catalyst |
| US6514479B1 (en) * | 1998-12-23 | 2003-02-04 | Institut Francais Du Petrole | EUO zeolite comprising crystals and aggregates of crystals with specific granulometrys and its use as a catalyst in the isomerisation of C8 aromatic compounds |
| CN1128672C (en) * | 1998-12-23 | 2003-11-26 | 法国石油公司 | EUO zeolite containing crystal and crytal aggregate with specific granular distribution and its use as catalyst of isomerized C8 aromatic compounds |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9242233B2 (en) | 2012-05-02 | 2016-01-26 | Saudi Basic Industries Corporation | Catalyst for light naphtha aromatization |
| US9782758B2 (en) | 2013-04-23 | 2017-10-10 | Saudi Basic Industries Corporation | Method of preparing hydrocarbon aromatization catalyst, the catalyst, and the use of the catalyst |
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