CN110026233A - A kind of method that ardealite extraction aluminium modified composite catalyst prepares propylene - Google Patents
A kind of method that ardealite extraction aluminium modified composite catalyst prepares propylene Download PDFInfo
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- CN110026233A CN110026233A CN201910331424.9A CN201910331424A CN110026233A CN 110026233 A CN110026233 A CN 110026233A CN 201910331424 A CN201910331424 A CN 201910331424A CN 110026233 A CN110026233 A CN 110026233A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention discloses a kind of ardealites to extract the method that aluminium modified composite catalyst prepares propylene, includes the following steps: the following steps are included: acidleach waste gypsum, separating-purifying aluminum is for γ-Al2O3, with γ-Al obtained2O3Sample is modified processing to ZSM-5, obtains composite catalyst, now comes into full contact with methanol liquid gasification with catalyst and reacts, obtains product propylene.On the one hand this method removes the partial impurities in ardealite, realize the recycling of ardealite solid waste, while utilizing the property of impurity itself, the γ-Al of preparation2O3The@ZSM-5 composite catalyst service life is long, and product propylene selection rate is high.
Description
Technical field
Aluminum is extracted the present invention relates to a kind of ardealite and is applied to methanol to propylene reaction research for composite material, belongs to third
Alkene preparation field.
Background technique
ZSM-5 catalyst reacts field in hydrocarbon catalytic cracking, has larger pore structure, and selectivity of light olefin compares
It is low.Carbon distribution synthesis speed and reaction temperature are exponentially increased relationship, so that catalyst life is short.In the dilute alkylation reaction of methanol,
There are many factor for influencing dilute hydrocarbon products formation, and wherein the acid strength and pore structure of catalyst are the crucial aspects of comparison, use list
One ZSM-5 catalyst product is selectively low.
Ardealite is phosphoric acid by wet process industry discarded object of power boiler discharge, produces 1t phosphoric acid by wet process (with P2O5Meter) will generate 4.5~
5.0t ardealite.Currently, Chinese ardealite average utilization is less than 10%, remaining ardealite still air storage cinder field, largely
Ardealite, which arbitrarily discharges, not only polluted environment, but also also take up a large amount of soil, and there are potential environmentally friendly risks.In addition, annual
Problem is stacked in order to handle ardealite, needs the problem of spending a large amount of cost, consuming money effort, can't resolve essence.Phosphorus stone
Cream usually requires the impurity that pretreatment removes Al etc. in fixed-end forces, mainly take at present water-washing method to ardealite at
Reason, but this method mainly removes soluble P, and there is also some valuable foreign ions in ardealite.
Summary of the invention
It is an object of the invention in view of the above-mentioned problems, according to ardealite in addition to principal component calcium sulfate also phosphoric acid, aluminium,
The impurity such as silicon, iron, current acid-base precipitation method extract the aluminium in ardealite impurity and AlCl are made3·6H2O synthesizes γ-with template
Al2O3γ-Al is compounded to form with ZSM-5 catalyst2O3@ZSM-5 composite catalyst, to solve single ZSM-5 in MTP reaction
Service life is short, the low problem of selectivity.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of method that ardealite extraction aluminium modified composite catalyst prepares propylene, comprising the following steps:
Step 1: the preparation of composite catalyst
Step 1.1: dilute hydrochloric acid acidleach waste gypsum: being added to the waste gypsum powder after drying according to liquid-solid ratio 20mL/g
In, leaching 1h at being 80 DEG C in acidleach temperature, centrifugation takes supernatant that sodium hydroxide solution is added, is separated by solid-liquid separation, is taken
Dilute hydrochloric acid is added in its supernatant, until white precipitate all dissolves, generates liquor alumini chloridi, evaporation and concentration, crystallisation by cooling, mistake
Filter, obtains AlCl3·6H2O solution；
Step 1.2: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=12.9-13.2:1-3, will
Cetyl trimethylammonium bromide CTAB is added to the AlCl of step 1.1 preparation3·6H2In O solution, stirring to dissolution, with wriggling
Pump is with 5mLmin-1Rate be pumped into 3molL-1Precipitating reagent to solution system pH value be 8-9, continue stir 30min, 80
DEG C water-bath aging 3h, be cooled to room temperature, filter, washing, quasi- boehmite sample, 600 DEG C of roasting 3h are made in 80 DEG C of dry 6h~12h
γ-Al is made2O3Sample；
Step 1.3: by γ-Al obtained in step 1.22O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent；
Step 2: the preparation of propylene:
Step 2.1: the composite catalyst of step 1.3 being fitted into fixed bed catalyst pipe, into fixed bed catalyst pipe
It is passed through nitrogen, reaction pressure 0.5MPa-1.0MPa, reaction temperature is 310 DEG C -430 DEG C；
Step 2.2: under the action of carrier gas nitrogen, with peristaltic pump by configured methanol solution with air speed 2.0h-1Conveying
To fixed bed catalyst pipe, methanol solution becomes methanol gas under high temperature, comes into full contact with and reacts with catalyst, obtains product third
Alkene.Further by product condensation, separation foreign gas, the higher propylene of degree of purity is obtained.
Further, dilute hydrochloric acid concentration is 1mol/L in step 1.1.
Further, the γ-Al in step 1.22O3Sample mesh number is 200 mesh, obtained by being ground up, sieved.
Further, the precipitating reagent in step 1.2 is NH3·H2O、Na2CO3Or NaHCO3One of.
Further, in step 1.3 modification method are as follows: according to mol ratio Si:Al:TPAOH:H2O=360:
1:19:8077, by sodium metaaluminate be added deionized water in, under continuous stirring, sequentially add tetrapropylammonium hydroxide TPAOH and
Ethyl orthosilicate is made ZSM-5 precursor mixed solution, after aging 8-24h, by γ-Al2O3With ZSM-5 1-3:1-3 in mass ratio
Mixed liquor, 180 DEG C of reaction 2h of microwave hydrothermal is added, cooling is filtered, washed, 105~110 DEG C of dry 6h~12h, 450 DEG C~
650 DEG C of roasting 3h complete modified obtained γ-Al2O3@ZSM-5 composite catalyst.
Further, in step 1.3 modification processing method, ageing time 12h.
Further, in step 1.3 modification processing method, γ-Al2O3It is in mass ratio 1:1 proportion with ZSM-5.
Further, in step 1.3 modification processing method, maturing temperature is 500 DEG C -600 DEG C.
Further, methanol solution by water and methanol molar ratio is H in step 2.32O:CH3OH=1:1 is configured.
By the γ-Al of preparation2O3@ZSM-5 composite catalyst is applied to methanol and prepares in the production technology of propylene, modified
The B acid and γ-Al of the ZSM-5 composite catalyst of composite catalyst2O3L acid can form B acid-L acid corrdination centre and B acid-L
Alkali center, and then enhance the bottleneck problem of the absorption dissociation degree under methanol lower temperature and the quick carbon distribution inactivation of catalyst；Separately
The micropore and γ-Al of one side ZSM-52O3It is mesoporous can form special hierarchical structure, and then weaken the diffusion of molecule, alleviate
ZSM-5 molecular sieve carbon distribution is formed, and catalyst life is extended；Meanwhile the special microcellular structure of ZSM-5 is conducive to strengthen composite catalyst
Restriction effect, and then improve target product selectivity.
Compared with prior art, the present invention having apparent beneficial effect, as can be known from the above technical solutions: the present invention is proposed
A kind of γ-Al2O3@ZSM-5 composite catalyst and preparation method thereof, it can product can be improved in the service life for improving catalyst again
The selectivity of propylene.
Below by specific embodiment, the invention will be further described.
Specific embodiment
Comparative example 1: unmodified ZSM-5 catalyst is applied to methanol to propylene reaction.
The preparation of ZSM-5 catalyst: according to molar ratio Si:Al:TPAOH:H2O=360:1:19:8077, will be inclined under room temperature
Sodium aluminate is added in deionized water, under lasting stirring, sequentially adds tetrapropylammonium hydroxide and the obtained mixing of ethyl orthosilicate is molten
Liquid, after aging 12h, 180 DEG C of reaction 2h of microwave hydrothermal are cooling, be filtered, washed, 105~110 DEG C of dry 6h~12h, and 550 DEG C roast
3h is burnt, ZSM-5 catalyst is made.
ZSM-5 catalyst is applied in process for preparing propylene from methanol, reaction pressure: normal pressure, reaction temperature: 380 DEG C, when heavy
Air speed: 2h-1, nitrogen flow rate: 20mLmin-1, H2O:CH3OH molar ratio 1:1, measures propylene hydrocarbon-selective 37.8%, service life
6.2h。
Embodiment 1
Step 1.1: dilute hydrochloric acid acidleach waste gypsum: being added to the waste gypsum powder after drying according to liquid-solid ratio 20mL/g
In, leaching 1h at being 80 DEG C in acidleach temperature, centrifugation takes supernatant, and it is molten that sodium hydroxide is added in obtained supernatant
Liquid is separated by solid-liquid separation, and takes its supernatant that dilute hydrochloric acid is added, until white precipitate all dissolves, generates liquor alumini chloridi, evaporation
Concentration, crystallisation by cooling, filtering, obtain AlCl3·6H2O；Wherein dilute hydrochloric acid concentration is 1mol/L,
Step 1.2: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=12.9-13.2:1-3, will
Cetyl trimethylammonium bromide CTAB is added to the AlCl of step 1.1 preparation3·6H2In O solution, stirring to dissolution, with wriggling
Pump is with 5mLmin-1Rate be pumped into 3molL-1NH3·H2O precipitating reagent to solution system pH value is 8-9, continues to stir
30min, 80 DEG C of water-bath aging 3h, it is cooled to room temperature, filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, 600
DEG C roasting 3h be made γ-Al2O3Sample, by γ-Al2O3Sample is ground up, sieved to 200 mesh of mesh number；
Step 1.3: by γ-Al obtained in step 1.22O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent；The method of modification are as follows: according to mol ratio Si:Al:TPAOH:H2Sodium metaaluminate is added O=360:1:19:8077
In deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and ZSM-5 forerunner is made in ethyl orthosilicate
Body mixed solution, after aging 12h, by γ-Al2O3Mixed liquor, 180 DEG C of microwave hydrothermal reactions are added with ZSM-5 1:1 in mass ratio
2h, cooling are filtered, washed, 105~110 DEG C of dry 6h~12h, 450 DEG C of roasting 3h, that is, complete modified obtained γ-Al2O3@
ZSM-5 composite catalyst.
Step 2: the preparation of propylene:
Step 2.1: the composite catalyst of step 1.3 being fitted into fixed bed catalyst pipe, into fixed bed catalyst pipe
It is passed through nitrogen, reaction pressure 0.5MPa-1.0MPa, reaction temperature is 310 DEG C -430 DEG C；
Step 2.2: under the action of carrier gas nitrogen, with peristaltic pump by configured methanol solution with air speed 2.0h-1Conveying
To fixed bed catalyst pipe, methanol solution becomes methanol gas under high temperature, comes into full contact with and reacts with catalyst, obtains product third
Alkene, the selectivity of propylene is 38.8%, composite catalyst service life 7.8h, than using unmodified ZSM-5 catalyst, product selection
Property improves 1.0%, catalyst life 1.6h.
Embodiment 2
Step 1.1: dilute hydrochloric acid acidleach waste gypsum: being added to the waste gypsum powder after drying according to liquid-solid ratio 20mL/g
In, leaching 1h at being 80 DEG C in acidleach temperature, centrifugation takes supernatant, and it is molten that sodium hydroxide is added in obtained supernatant
Liquid is separated by solid-liquid separation, and takes its supernatant that dilute hydrochloric acid is added, until white precipitate all dissolves, generates liquor alumini chloridi, evaporation
Concentration, crystallisation by cooling, filtering, obtain AlCl3·6H2O solution；Wherein dilute hydrochloric acid concentration is 1mol/L,
Step 1.2: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=12.9-13.2:1-3, will
Cetyl trimethylammonium bromide CTAB is added to the AlCl of step 1.1 preparation3·6H2In O solution, stirring to dissolution, with wriggling
Pump is with 5mLmin-1Rate be pumped into 3molL-1NH3·H2O precipitating reagent to solution system pH value is 8-9, continues to stir
30min, 80 DEG C of water-bath aging 3h, it is cooled to room temperature, filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, 600
DEG C roasting 3h be made γ-Al2O3Sample, by γ-Al2O3Sample is ground up, sieved to 200 mesh of mesh number；
Step 1.3: by γ-Al obtained in step 1.22O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent；The method of modification are as follows: according to mol ratio Si:Al:TPAOH:H2Sodium metaaluminate is added O=360:1:19:8077
In deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and ZSM-5 forerunner is made in ethyl orthosilicate
Body mixed solution, after aging 12h, by γ-Al2O3Mixed liquor, 180 DEG C of microwave hydrothermal reactions are added with ZSM-5 1:1 in mass ratio
2h, cooling are filtered, washed, 105~110 DEG C of dry 6h~12h, 500 DEG C of roasting 3h, that is, complete modified obtained γ-Al2O3@
ZSM-5 composite catalyst.
Step 2: the preparation of propylene:
Step 2.1: the composite catalyst of step 1.3 being fitted into fixed bed catalyst pipe, into fixed bed catalyst pipe
It is passed through nitrogen, reaction pressure 0.5MPa-1.0MPa, reaction temperature is 310 DEG C -430 DEG C；
Step 2.2: under the action of carrier gas nitrogen, with peristaltic pump by configured methanol solution with air speed 2.0h-1Conveying
To fixed bed catalyst pipe, methanol solution becomes methanol gas under high temperature, comes into full contact with and reacts with catalyst, obtains product third
Alkene, the selectivity of propylene is 40.6%, composite catalyst service life 9.5h, than using unmodified ZSM-5 catalyst, product selection
Property improves 2.8%, catalyst life 3.3h.
Embodiment 3
Step 1.1: dilute hydrochloric acid acidleach waste gypsum: being added to the waste gypsum powder after drying according to liquid-solid ratio 20mL/g
In, leaching 1h at being 80 DEG C in acidleach temperature, centrifugation takes supernatant, and it is molten that sodium hydroxide is added in obtained supernatant
Liquid is separated by solid-liquid separation, and takes its supernatant that dilute hydrochloric acid is added, until white precipitate all dissolves, generates liquor alumini chloridi, evaporation
Concentration, crystallisation by cooling, filtering, obtain AlCl3·6H2O solution；Wherein dilute hydrochloric acid concentration is 1mol/L,
Step 1.2: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=12.9-13.2:1-3, will
Cetyl trimethylammonium bromide CTAB is added to the AlCl of step 1.1 preparation3·6H2In O solution, stirring to dissolution, with wriggling
Pump is with 5mLmin-1Rate be pumped into 3molL-1NH3·H2O precipitating reagent to solution system pH value is 8-9, continues to stir
30min, 80 DEG C of water-bath aging 3h, it is cooled to room temperature, filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, 600
DEG C roasting 3h be made γ-Al2O3Sample, by γ-Al2O3Sample is ground up, sieved to 200 mesh of mesh number；
Step 1.3: by γ-Al obtained in step 1.22O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent；The method of modification are as follows: according to mol ratio Si:Al:TPAOH:H2Sodium metaaluminate is added O=360:1:19:8077
In deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and ZSM-5 forerunner is made in ethyl orthosilicate
Body mixed solution, after aging 12h, by γ-Al2O3Mixed liquor, 180 DEG C of microwave hydrothermal reactions are added with ZSM-5 1:1 in mass ratio
2h, cooling are filtered, washed, 105~110 DEG C of dry 6h~12h, 550 DEG C of roasting 3h, that is, complete modified obtained γ-Al2O3@
ZSM-5 composite catalyst.
Step 2: the preparation of propylene:
Step 2.1: the composite catalyst of step 1.3 being fitted into fixed bed catalyst pipe, into fixed bed catalyst pipe
It is passed through nitrogen, reaction pressure 0.5MPa-1.0MPa, reaction temperature is 310 DEG C -430 DEG C；
Step 2.2: under the action of carrier gas nitrogen, with peristaltic pump by configured methanol solution with air speed 2.0h-1Conveying
To fixed bed catalyst pipe, methanol solution becomes methanol gas under high temperature, comes into full contact with and reacts with catalyst, obtains product third
Alkene, the selectivity of propylene is 58.58%, composite catalyst service life 15.6h, than using unmodified ZSM-5 catalyst, product choosing
Selecting property improves 20.78%, catalyst life 9.4h.
Embodiment 4
Step 1.1: dilute hydrochloric acid acidleach waste gypsum: being added to the waste gypsum powder after drying according to liquid-solid ratio 20mL/g
In, leaching 1h at being 80 DEG C in acidleach temperature, centrifugation takes supernatant, and it is molten that sodium hydroxide is added in obtained supernatant
Liquid is separated by solid-liquid separation, and takes its supernatant that dilute hydrochloric acid is added, until white precipitate all dissolves, generates liquor alumini chloridi, evaporation
Concentration, crystallisation by cooling, filtering, obtain AlCl3·6H2O solution；Wherein dilute hydrochloric acid concentration is 1mol/L,
Step 1.2: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=12.9-13.2:1-3, will
Cetyl trimethylammonium bromide CTAB is added to the AlCl of step 1.1 preparation3·6H2In O solution, stirring to dissolution, with wriggling
Pump is with 5mLmin-1Rate be pumped into 3molL-1NH3·H2O precipitating reagent to solution system pH value is 8-9, continues to stir
30min, 80 DEG C of water-bath aging 3h, it is cooled to room temperature, filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, 600
DEG C roasting 3h be made γ-Al2O3Sample, by γ-Al2O3Sample is ground up, sieved to 200 mesh of mesh number；
Step 1.3: by γ-Al obtained in step 1.22O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent；The method of modification are as follows: according to mol ratio Si:Al:TPAOH:H2Sodium metaaluminate is added O=360:1:19:8077
In deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and ZSM-5 forerunner is made in ethyl orthosilicate
Body mixed solution, after aging 12h, by γ-Al2O3Mixed liquor, 180 DEG C of microwave hydrothermal reactions are added with ZSM-5 1:1 in mass ratio
2h, cooling are filtered, washed, 105~110 DEG C of dry 6h~12h, 600 DEG C of roasting 3h, that is, complete modified obtained γ-Al2O3@
ZSM-5 composite catalyst.
Step 2: the preparation of propylene:
Step 2.1: the composite catalyst of step 1.3 being fitted into fixed bed catalyst pipe, into fixed bed catalyst pipe
It is passed through nitrogen, reaction pressure 0.5MPa-1.0MPa, reaction temperature is 310 DEG C -430 DEG C；
Step 2.2: under the action of carrier gas nitrogen, with peristaltic pump by configured methanol solution with air speed 2.0h-1Conveying
To fixed bed catalyst pipe, methanol solution becomes methanol gas under high temperature, comes into full contact with and reacts with catalyst, obtains product third
Alkene, the selectivity of propylene is 43.9%, composite catalyst service life 9.6h, than using unmodified ZSM-5 catalyst, product selection
Property improves 6.1%, catalyst life 3.4h.
Embodiment 5
Step 1.1: dilute hydrochloric acid acidleach waste gypsum: being added to the waste gypsum powder after drying according to liquid-solid ratio 20mL/g
In, leaching 1h at being 80 DEG C in acidleach temperature, centrifugation takes supernatant, and it is molten that sodium hydroxide is added in obtained supernatant
Liquid is separated by solid-liquid separation, and takes its supernatant that dilute hydrochloric acid is added, until white precipitate all dissolves, generates liquor alumini chloridi, evaporation
Concentration, crystallisation by cooling, filtering, obtain AlCl3·6H2O solution；Wherein dilute hydrochloric acid concentration is 1mol/L,
Step 1.2: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=12.9-13.2:1-3, will
Cetyl trimethylammonium bromide CTAB is added to the AlCl of step 1.1 preparation3·6H2In O solution, stirring to dissolution, with wriggling
Pump is with 5mLmin-1Rate be pumped into 3molL-1NH3·H2O precipitating reagent to solution system pH value is 8-9, continues to stir
30min, 80 DEG C of water-bath aging 3h, it is cooled to room temperature, filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, 600
DEG C roasting 3h be made γ-Al2O3Sample, by γ-Al2O3Sample is ground up, sieved to 200 mesh of mesh number；
Step 1.3: by γ-Al obtained in step 1.22O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent；The method of modification are as follows: according to mol ratio Si:Al:TPAOH:H2Sodium metaaluminate is added O=360:1:19:8077
In deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and ZSM-5 forerunner is made in ethyl orthosilicate
Body mixed solution, after aging 12h, by γ-Al2O3Mixed liquor, 180 DEG C of microwave hydrothermal reactions are added with ZSM-5 1:1 in mass ratio
2h, cooling are filtered, washed, 105~110 DEG C of dry 6h~12h, 650 DEG C of roasting 3h, that is, complete modified obtained γ-Al2O3@
ZSM-5 composite catalyst.
Step 2: the preparation of propylene:
Step 2.1: the composite catalyst of step 1.3 being fitted into fixed bed catalyst pipe, into fixed bed catalyst pipe
It is passed through nitrogen, reaction pressure 0.5MPa-1.0MPa, reaction temperature is 310 DEG C -430 DEG C；
Step 2.2: under the action of carrier gas nitrogen, with peristaltic pump by configured methanol solution with air speed 2.0h-1Conveying
To fixed bed catalyst pipe, methanol solution becomes methanol gas under high temperature, comes into full contact with and reacts with catalyst, obtains product third
Alkene, the selectivity of propylene is 36.8%, composite catalyst service life 5.8h, than using unmodified ZSM-5 catalyst, product selection
Property reduces 1.0%, the short 0.4h of catalyst life.
Claims (9)
1. a kind of ardealite extracts the method that aluminium modified composite catalyst prepares propylene, which comprises the following steps:
Step 1: the preparation of composite catalyst
Step 1.1: dilute hydrochloric acid: being added in the waste gypsum powder after drying by acidleach waste gypsum according to liquid-solid ratio 20mL/g,
Acidleach temperature is leaching 1h at 80 DEG C, and centrifugation takes supernatant that sodium hydroxide solution is added, is separated by solid-liquid separation, taken thereon
Dilute hydrochloric acid is added in clear liquid, until white precipitate all dissolves, generates liquor alumini chloridi, evaporation and concentration, crystallisation by cooling, filtering obtain
AlCl3·6H2O solution；
Step 1.2: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=12.9-13.2:1-3, by hexadecane
Base trimethylammonium bromide CTAB is added to the AlCl of step 1.1 preparation3·6H2In O solution, stirring to dissolution, with peristaltic pump with
5mL·min-1Rate be pumped into 3molL-1Precipitating reagent to solution system pH value be 8-9, continue stir 30min, 80 DEG C of water
Bath aging 3h, it is cooled to room temperature, filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, 600 DEG C of roasting 3h are made
γ-Al2O3Sample；
Step 1.3: by γ-Al obtained in step 1.22O3Sample is modified processing to ZSM-5, obtains composite catalyst；
Step 2: the preparation of propylene:
Step 2.1: the composite catalyst of step 1.3 being fitted into fixed bed catalyst pipe, is passed through into fixed bed catalyst pipe
Nitrogen, reaction pressure 0.5MPa-1.0MPa, reaction temperature are 310 DEG C -430 DEG C；
Step 2.2: under the action of carrier gas nitrogen, with peristaltic pump by configured methanol solution with air speed 2.0h-1It is delivered to solid
In bed catalyst pipe, methanol solution becomes methanol gas under high temperature, comes into full contact with and reacts with catalyst, obtains product propylene.
2. a kind of ardealite according to claim 1 extracts the method that aluminium modified composite catalyst prepares propylene, special
Sign is that dilute hydrochloric acid concentration is 1mol/L in step 1.1.
3. a kind of ardealite according to claim 1 extracts the method that aluminium modified composite catalyst prepares propylene, special
Sign is, the γ-Al in step 1.22O3Sample mesh number is 200 mesh, obtained by being ground up, sieved.
4. a kind of ardealite according to claim 1 extracts the method that aluminium modified composite catalyst prepares propylene, special
Sign is that the precipitating reagent in step 1.2 is NH3·H2O、Na2CO3Or NaHCO3One of.
5. a kind of ardealite according to claim 1 extracts the method that aluminium modified composite catalyst prepares propylene, special
Sign is, the method for modification in step 1.3 are as follows: according to mol ratio Si:Al:TPAOH:H2O=360:1:19:8077,
Sodium metaaluminate is added in deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and ethyl orthosilicate
ZSM-5 precursor mixed solution is made, after aging 8-24h, by γ-Al2O3It is mixed with ZSM-5 1-3:1-3 in mass ratio addition
Liquid, 180 DEG C of reaction 2h of microwave hydrothermal, cooling are filtered, washed, 105~110 DEG C of dry 6h~12h, 450 DEG C~650 DEG C roastings
3h completes modified obtained γ-Al2O3@ZSM-5 composite catalyst.
6. a kind of ardealite according to claim 5 extracts the method that aluminium modified composite catalyst prepares propylene, special
Sign is, in step 1.3 modification processing method, ageing time 12h.
7. a kind of ardealite according to claim 5 extracts the method that aluminium modified composite catalyst prepares propylene, special
Sign is, in step 1.3 modification processing method, γ-Al2O3It is in mass ratio 1:1 proportion with ZSM-5.
8. a kind of ardealite according to claim 5 extracts the method that aluminium modified composite catalyst prepares propylene, special
Sign is, in step 1.3 modification processing method, maturing temperature is 500 DEG C -600 DEG C.
9. a kind of ardealite according to claim 1 extracts the method that aluminium modified composite catalyst prepares propylene, special
Sign is that methanol solution is H by water and methanol molar ratio in step 2.32O:CH3OH=1:1 is configured.
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| CN115259982A (en) * | 2022-08-01 | 2022-11-01 | 润和催化剂股份有限公司 | Process method and reaction system for preparing propylene by methanol conversion |
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| CN105772059A (en) * | 2014-12-26 | 2016-07-20 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene from methyl alcohol or/and dimethyl ether and preparation method of catalyst |
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| CN105772059A (en) * | 2014-12-26 | 2016-07-20 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene from methyl alcohol or/and dimethyl ether and preparation method of catalyst |
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| 王冠超等: "γ-Al2O3预处理方式对γ-Al2O3/SAPO-34复合催化剂物化性质及催化性能的影响", 《人工晶体学报》 * |
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| CN115259982A (en) * | 2022-08-01 | 2022-11-01 | 润和催化剂股份有限公司 | Process method and reaction system for preparing propylene by methanol conversion |
| CN115259982B (en) * | 2022-08-01 | 2024-05-14 | 润和催化剂股份有限公司 | Technological method and reaction system for preparing propylene by methanol conversion |
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