CN107812539A - A kind of methanol alkylation produces the preparation method of paraxylene catalyst - Google Patents
A kind of methanol alkylation produces the preparation method of paraxylene catalyst Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/16—Copper
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a kind of methanol alkylation to prepare paraxylene catalyst method, Pt（acac）2、Fe（acac）2, Cu BTC, tetrahydrofuran, tetrahydrofuran borine, Cu（NO3）2·3H2O, BTC is primary raw material, in the presence of supercritical carbon dioxide is fluid media (medium), using postcritical metallic compound as presoma, Cu BTC porous materials are carrier, and boranes are reducing agent, reaction obtains porous material loading binary or polynary nanometer alloy catalyst, the present invention is reacted by methanol alkylation, is obtained paraxylene, is saved the step such as isomerization in traditional handicraft, process route shortens, and paraxylene once through yield greatly improves.
Description
Technical field
The present invention relates to the fluid catalyst and its system that a kind of benzene and methanol alkylation high selectivity produce paraxylene
Preparation Method, belong to catalyst technical field.
Background technology
Paraxylene is particularly important large industrial chemicals, mainly for the production of terephthalic acid (TPA) and terephthalic acid (TPA) two
First vinegar.Because PET industry development in China's is swift and violent, drive and the growth of consumption figure, so as to cause the consumption figure of paraxylene
Rapid growth.Industrially aromatics seperation, toluene disproportionation or heavy aromatics transalkylation are carried out generally by petroleum cracking product
Method produces paraxylene, and due to these substantial amounts of benzene of method by-product, and the economic value of benzene is low, to a certain extent influence pair
The economy of dimethylbenzene preparation technology.Conventional method uses bed technology more, and bed temperature is uneven, catalyst stability
Difference, easily inactivate and be not easy regeneration to improve catalyst stability, it is during the course of the reaction to need to be passed through hydrogen as carrier gas more, and
Hydrogen has a higher value in itself, thus cost it is higher on；The preparation of catalyst and modification procedure are cumbersome, costly above-mentioned
The conversion ratio of benzene is more between 30% one 40% in technology, and raw material availability is not high enough.
The content of the invention
It is an object of the invention to provide the preparation method that a kind of methanol alkylation produces paraxylene catalyst, to diformazan
Selectivity of the benzene in xylene isomer increases substantially, and eliminates the step such as isomerization in traditional handicraft, process route contracting
Short, paraxylene once through yield greatly improves.
A kind of methanol alkylation produces the preparation method of paraxylene catalyst, and this method comprises the following steps：
Step 1, the Pt by gross mass for 50mg（acac）2And Fe（acac）2Presoma is put into the reactor that volume is 20ml,
Described Pt（acac）2And Fe（acac）2Material amount ratio be 1:1；
Step 2,20g Cu-BTC nano-porous materials are put into reactor, then add 500 μ L tetrahydrofuran in reaction
In kettle, capping kettle, 150atm supercritical CO is pressed into2In reactor, 60 DEG C are heated to, and after being incubated 2h, is slowly let out
Pressure, obtain nano-porous materials supporting Pt and the preparation of Fe presomas；
Step 3, above-mentioned presoma is put into reactor, adds 1mL tetrahydrofuran borines, capping kettle, be pressed into 150atm
Supercritical CO2In reactor, 80 DEG C are heated to, and after being incubated 2h, reaction terminates, and after naturally cooling to room temperature, slowly lets out
It is depressed into normal pressure；
The supercritical CO of step 4, continuous press-in 80mL2In reactor, and with 0.5ml/min speed pressure release, after continuing 2h
Stop, Cu-BTC supporting Pt Fe nanometer alloy catalysts can be obtained by taking out sample.
Described Cu-BTC nano-porous materials preparation methods are as follows：
Step 1, import Cu into Teflon reactors（NO3）2·3H2O, 1,3,5 1 benzenetricarboxylic acid（BTC）With as solvent
Distilled water and ethanol, ultimately form mol ratio Cu：BTC：Ethanol：H2O=1：0.56：55.6：186 reactant mixture：
Step 2, said mixture is subjected to ultrasonic irradiation pretreatment 5 minutes at room temperature, so that reactant mixture homogeneous, from
And promote nucleation；
Step 3, above-mentioned pretreated Teflon reactors will be contained installed in microwave reactor by manufacture, irradiating
2.45GHz microwave 2 minutes, 140 DEG C are risen to by temperature：
Step 4, by keeping 30 minutes at a temperature of reactant mixture/140 DEG C to carry out crystallization reaction, be subsequently cooled to room temperature,
And filtered with filter-paper filter, to obtain powdered product, washed 3 times with 70 DEG C of ethanol, to purify obtained powdered product,
Then dried at 100 DEG C, so as to obtain hydridization Cu-BTC nano-porous materials.
Beneficial effect：Catalyst of the present invention is in the presence of supercritical carbon dioxide is fluid media (medium), with postcritical metallization
Compound is presoma, and Cu-BTC porous materials are carrier, and boranes are reducing agent, and reaction obtains porous material loading binary or more
First nanometer alloy catalyst；Supercritical CO2Similar gas has compressibility, and cascading water, Er Qieyou can occur as gas
With similar liquids mobility therefore some overcritical middle dissolving metal precursor can with it is overcritical with carry
The full and uniform mixing of body, after reducing agent reduces, nano particle can depart from overcritical and load on carrier；Catalytic activity
Nano particle is not distributed only over the surface of carrier, can also be distributed in hole, in addition it is mesoporous in, thus there is higher catalysis
Activity and stability so that selectivity of the paraxylene in xylene isomer increases substantially, and up to more than 95% is right
Dimethylbenzene once through yield is up to more than 20%, eliminates the step such as isomerization in traditional handicraft, process route shortens, to two
Toluene once through yield greatly improves.
Embodiment
Embodiment 1
A kind of methanol alkylation produces the preparation method of paraxylene catalyst, comprises the following steps：
Step 1, the Pt by gross mass for 50mg（acac）2And Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2And Fe（acac）2Material amount ratio be 1:1；
Step 2,20g Cu-BTC nano-porous materials are put into reactor, then add 500 μ L tetrahydrofuran in reaction
In kettle, capping kettle, 150atm supercritical CO is pressed into2In reactor, 60 DEG C are heated to, and after being incubated 2h, is slowly let out
Pressure, obtain nano-porous materials supporting Pt and the preparation of Fe presomas；
Step 3, above-mentioned presoma is put into reactor, adds 1mL tetrahydrofuran borines, capping kettle, be pressed into 150atm
Supercritical CO2In reactor, 80 DEG C are heated to, and after being incubated 2h, reaction terminates, and after naturally cooling to room temperature, slowly lets out
It is depressed into normal pressure；
The supercritical CO of step 4, continuous press-in 80mL2In reactor, and with 0.5ml/min speed pressure release, after continuing 2h
Stop, Cu-BTC supporting Pt Fe nanometer alloy catalysts can be obtained by taking out sample.
Described Cu-BTC nano-porous materials preparation methods are as follows：
Step 1, import Cu into Teflon reactors（NO3）2·3H2O, 1,3,5 1 benzenetricarboxylic acid（BTC）With as solvent
Distilled water and ethanol, ultimately form mol ratio Cu：BTC：Ethanol：H2O=1：0.56：55.6：186 reactant mixture：
Step 2, said mixture is subjected to ultrasonic irradiation pretreatment 5 minutes at room temperature, so that reactant mixture homogeneous, from
And promote nucleation；
Step 3, above-mentioned pretreated Teflon reactors will be contained installed in microwave reactor by manufacture, irradiating
2.45GHz microwave 2 minutes, 140 DEG C are risen to by temperature：
Step 4, by keeping 30 minutes at a temperature of reactant mixture/140 DEG C to carry out crystallization reaction, be subsequently cooled to room temperature,
And filtered with filter-paper filter, to obtain powdered product, washed 3 times with 70 DEG C of ethanol, to purify obtained powdered product,
Then dried at 100 DEG C, so as to obtain hydridization Cu-BTC nano-porous materials.
Embodiment 2
Step 1, the Pt by gross mass for 30mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 1:1；
Remaining step is the same as embodiment 1.
Embodiment 3
Step 1, the Pt by gross mass for 15mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 1:1；
Remaining step is the same as embodiment 1.
Embodiment 4
Step 1, the Pt by gross mass for 100mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 1:1；
Remaining step is the same as embodiment 1.
Embodiment 5
Step 1, the Pt by gross mass for 200mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 1:1；
Remaining step is the same as embodiment 1.
Embodiment 6
Step 1, the Pt by gross mass for 50mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 10:1；
Remaining step is the same as embodiment 1.
Embodiment 7
Step 1, the Pt by gross mass for 50mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 1:10；
Remaining step is the same as embodiment 1.
Embodiment 8
Step 1, the Pt by gross mass for 50mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 7:1；
Remaining step is the same as embodiment 1.
Embodiment 9
Step 1, the Pt by gross mass for 50mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 1:7；
Remaining step is the same as embodiment 1.
Embodiment 10
Step 1, the Pt by gross mass for 50mg（acac）2Fe（acac）2The reactor that volume is 20ml is put into presoma
In, described Pt（acac）2Fe（acac）2Material amount ratio be 2:1.
Embodiment 11
Step 2,20g Cu-BTC nano-porous materials and 15g cross-linked rectorite/SAPO-34 composites are put into reactor
In, 500 μ L tetrahydrofuran is then added in reactor, capping kettle, is pressed into 150atm supercritical CO2In reactor
In, 60 DEG C are heated to, and after being incubated 2h, slow pressure release, obtain nano-porous materials supporting Pt and the preparation of Fe presomas；
The preparation method of described cross-linked rectorite/SAPO-34 composites is as follows：
After 15 parts of SAPO-34 and 5 part of cross-linked rectorites are dried, crushing is ground, 600 mesh sieve, and are mixed at 90 DEG C
Uniformly, it is dispersed in the deionized water solution of ethanol one, adds 14 parts of cetyl trimethylammonium bromides in 60 DEG C of stirred in water bath 4
Hour, ultrasonic disperse 30 minutes, filter, washing, be dried under vacuum to constant weight, grind, sieve and produce cross-linked rectorite/SAPO-34
Composite.
Reference examples 1
It is with the difference of embodiment 1：In the step 2 of catalyst preparation, 250 μ L tetrahydrofuran is added in reactor, envelope
Reactor is closed, is pressed into 150atm supercritical CO2In reactor, remaining step is identical with embodiment 1.
Reference examples 2
It is with the difference of embodiment 1：In the step 2 of catalyst preparation, 750 μ L tetrahydrofuran is added in reactor, envelope
Reactor is closed, is pressed into 150atm supercritical CO2In reactor, remaining step is identical with embodiment 1.
Reference examples 3
It is with the difference of embodiment 1：In the step 3 of catalyst preparation, add 0.1mL tetrahydrofuran borines, remaining step with
Embodiment 1 is identical.
Reference examples 4
It is with the difference of embodiment 1：In the step 3 of catalyst preparation, add 0.5mL tetrahydrofuran borines, remaining step with
Embodiment 1 is identical.
Reference examples 5
It is with the difference of embodiment 1：In the step 4 of catalyst preparation, with 0.1ml/min speed pressure release, remaining step with
Embodiment 1 is identical.
Reference examples 6
It is with the difference of embodiment 1：In the step 4 of catalyst preparation, with 1ml/min speed pressure release, remaining step and reality
It is identical to apply example 1.
Reference examples 7
It is with the difference of embodiment 1：In Cu-BTC nano-porous materials preparation process 1, mol ratio Cu：BTC：Ethanol：H2O=
1：0.1：50：200, remaining step is identical with embodiment 1.
Reference examples 8
It is with the difference of embodiment 1：In Cu-BTC nano-porous materials preparation process 1, mol ratio Cu：BTC：Ethanol：H2O=
1：1：10：100, remaining step is identical with embodiment 1.
Reference examples 9
It is with the difference of embodiment 1：In Cu-BTC nano-porous materials preparation process 3,1.45GHz microwave is irradiated 2 minutes,
Remaining step is identical with embodiment 1.
Reference examples 10
It is with the difference of embodiment 1：In Cu-BTC nano-porous materials preparation process 3,0.45GHz microwave is irradiated 2 minutes,
Remaining step is identical with embodiment 1.
Reference examples 11
It is with the difference of embodiment 1：Add be not Cu-BTC nano-porous materials but Fe-BTC nano-porous materials,
Fe-BTC nano-porous materials preparation methods are as follows：
Step 1, import Fe into Teflon reactors（NO3）2·3H2O, 1,3,5 1 benzenetricarboxylic acid（BTC）With as solvent
Distilled water and ethanol, ultimately form mol ratio Cu：BTC：Ethanol：H2O=1：0.56：55.6：186 reactant mixture：
Step 2, said mixture is subjected to ultrasonic irradiation pretreatment 5 minutes at room temperature, so that reactant mixture homogeneous, from
And promote nucleation；
Step 3, above-mentioned pretreated Teflon reactors will be contained installed in microwave reactor by manufacture, irradiating
2.45GHz microwave 2 minutes, 140 DEG C are risen to by temperature：
Step 4, by keeping 30 minutes at a temperature of reactant mixture/140 DEG C to carry out crystallization reaction, be subsequently cooled to room temperature,
And filtered with filter-paper filter, to obtain powdered product, washed 3 times with 70 DEG C of ethanol, to purify obtained powdered product,
Then dried at 100 DEG C, so as to obtain Fe-BTC nano-porous materials
Benzene and methanol alkylation reaction are carried out on fluidized bed reaction.Reaction condition is：Catalyst packing 100g, reaction temperature
Spend for 500 DEG C, benzene feedstock and methanol molar ratio are 1：2, raw material weight (hourly) space velocity (WHSV) is 2.8h-1, reaction pressure 0.1MPa, reaction production
Thing is analyzed with online gas-chromatography, and as a result it is as shown in the table.
Test result indicates that in the presence of supercritical carbon dioxide is fluid media (medium), using postcritical metallic compound as forerunner
Body, Cu-BTC porous materials are carrier, and boranes are reducing agent, and reaction obtains porous material loading binary or polynary nanometer alloy
Catalyst has good catalytic effect, and in the timing of reaction condition one, Selectivity for paraxylene is higher, and catalytic performance is better, instead
It is poorer；In Pt（acac）2Fe（acac）2Addition be 50mg and the amount of material ratio is 1:When 1, other dispensings are fixed, and are urged
It is best to change effect, is with the difference of embodiment 1, embodiment 2 to embodiment 10 changes catalyst Pt respectively（acac）2Fe
（acac）2Dosage and proportioning, have different influences to the catalytic performance of catalyst, it should be noted that embodiment 11 adds
Cross-linked rectorite/SAPO-34 composites, Selectivity for paraxylene significantly improve, and illustrate that cross-linked rectorite/SAPO-34 is compound
Material has more preferable optimization function to the structure-activity of catalysis material；Reference examples 1 to reference examples 4 change tetrahydrofuran borine
With the injection rate of tetrahydrofuran, other steps are identical, cause the activity of catalyst to change, Selectivity for paraxylene is bright
It is aobvious to reduce；Reference examples 5 to reference examples 6 change pressure release speed, and Selectivity for paraxylene is not also high, illustrates that the height of pressure release speed is right
The load effect of metal influences very big；Reference examples 7 and reference examples 8, change the mol ratio of Cu-BTC raw materials, effect is still not
It is good；Reference examples 9 and the frequency of the microwave of reference examples 10 change, and cause the structural property of porous material to change, effect is bright
It is aobvious to be deteriorated；Therefore there is excellent catalytic effect to methanol alkylation reaction using catalyst prepared by the present invention.
Claims (2)
1. a kind of methanol alkylation produces the preparation method of paraxylene catalyst, it is characterised in that this method includes following step
Suddenly：
Step 1, the Pt by gross mass for 50mg（acac）2And Fe（acac）2Presoma is put into the reactor that volume is 20ml,
Described Pt（acac）2And Fe（acac）2The amount ratio of material is 1:1；
Step 2,20g Cu-BTC nano-porous materials are put into reactor, then add 500 μ L tetrahydrofuran in reaction
In kettle, capping kettle, 150atm supercritical CO is pressed into2In reactor, 60 DEG C are heated to, and after being incubated 2h, is slowly let out
Pressure, obtain nano-porous materials supporting Pt and the preparation of Fe presomas；
Step 3, above-mentioned presoma is put into reactor, adds 1mL tetrahydrofuran borines, capping kettle, be pressed into 150atm
Supercritical CO2In reactor, 80 DEG C are heated to, and after being incubated 2h, reaction terminates, and after naturally cooling to room temperature, slowly lets out
It is depressed into normal pressure；
The supercritical CO of step 4, continuous press-in 80mL2In reactor, and with 0.5ml/min speed pressure release, stop after continuing 2h
Only, Cu-BTC supporting Pt Fe nanometer alloy catalysts can be obtained by taking out sample.
2. a kind of methanol alkylation produces the preparation method of paraxylene catalyst according to claim 1, it is characterised in that
Described Cu-BTC nano-porous materials preparation methods are as follows：
Step 1, import Cu into Teflon reactors（NO3）2·3H2O, 1,3,5 1 benzenetricarboxylic acid（BTC）With as solvent
Distilled water and ethanol, ultimately form mol ratio Cu：BTC：Ethanol：H2O=1：0.56：55.6：186 reactant mixture：
Step 2, said mixture is subjected to ultrasonic irradiation pretreatment about 5 minutes at room temperature, so that reactant mixture homogeneous,
So as to promote to be nucleated；
Step 3, above-mentioned pretreated Teflon reactors will be contained installed in microwave reactor by manufacture, irradiating
2.45GHz microwave 2 minutes, 140 DEG C are risen to by temperature：
Step 4, by keeping 30 minutes at a temperature of reactant mixture/140 DEG C to carry out crystallization reaction, be subsequently cooled to room temperature,
And filtered with filter-paper filter, to obtain powdered product, washed 3 times with 70 DEG C of ethanol, to purify obtained powdered product,
Then dried at 100 DEG C, so as to obtain hydridization Cu-BTC nano-porous materials.
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