CN109999894A - A kind of ardealite extracts aluminum for the method for composite catalyst - Google Patents
A kind of ardealite extracts aluminum for the method for composite catalyst Download PDFInfo
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- CN109999894A CN109999894A CN201910331421.5A CN201910331421A CN109999894A CN 109999894 A CN109999894 A CN 109999894A CN 201910331421 A CN201910331421 A CN 201910331421A CN 109999894 A CN109999894 A CN 109999894A
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- 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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Abstract
The invention discloses a kind of ardealites to extract aluminum for the method for composite catalyst, 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.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 selectivity is high, while reducing reaction temperature.
Description
Technical field
The present invention relates to a kind of ardealites to extract aluminum for the method for composite catalyst, belongs to field of catalyst preparation.
Background technique
ZSM-5 catalyst is preparing other chemical products fields with methanol, has larger pore structure, and selectivity of product compares
It is low.Generally use it is modified prepare multi-stage porous molecular sieve methods ZSM-5 modified, so that its duct is become narrow, enhance shape-selective
Function, to improve selectivity of product.In addition, being prepared in other chemical products reaction process with methanol, temperature is mostly at 400 DEG C
More than, carbon distribution synthesis speed and reaction temperature are exponentially increased relationship, so that catalyst life is short.So modified compound
Catalyst, which can reduce system reaction temperature, can be effectively relieved carbon distribution synthesis speed, improve catalyst life, save the cost.
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 solves single ZSM-5 and is preparing it with methanol
The problem that the service life is short in the reaction of its chemical products, reaction temperature is high and selectivity is low.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of ardealite extracts aluminum for the method for composite catalyst, comprising the following steps:
Step 1: dilute hydrochloric acid: being added in the waste gypsum powder after drying by acidleach waste gypsum according to liquid-solid ratio 20mL/g,
Leaching 1h at being 80 DEG C in acidleach temperature, centrifugation take supernatant；
Step 2: separating-purifying aluminium: sodium hydroxide solution being added into the supernatant that step 1 obtains, and carries out solid-liquid point
From, its supernatant addition dilute hydrochloric acid is taken, until white precipitate all dissolves, generation liquor alumini chloridi, evaporation and concentration, cooling knot
Brilliant, filtering, obtains AlCl3·6H2O solution；Chemical equation is as follows:
Al2O3+ 2NaOH=2NaAlO2+H2O
There is white precipitate generation when dilute hydrochloric acid is just added:
HCl+NaAlO2+H2O=NaCl+Al (OH)3↓
With the addition of dilute hydrochloric acid, hydrochloric acid is gradually excessive, white precipitate dissolution:
Al(OH)3+ 3HCl=AlCl3(aq)+3H2O
Step 3: the preparation of composite catalyst:
Step 3.1: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=12.9-13.2:1-3, will
Cetyl trimethylammonium bromide CTAB is added to AlCl3·6H2In O solution, stir to dissolution, with peristaltic pump with 5mLmin-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, quasi- boehmite sample is made in 80 DEG C of dry 6h~12h, the obtained γ-Al of 600 DEG C of roasting 3h2O3Sample
Product；
Step 3.2: with γ-Al obtained in step 3.12O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent.
Further, dilute hydrochloric acid concentration is 1mol/L in step 1.
Further, the γ-Al in step 3.12O3Sample mesh number is 200 mesh, obtained by being ground up, sieved.
Further, the precipitating reagent in step 3.1 is NH3·H2O、Na2CO3Or NaHCO3One of.
Further, in step 3.2 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 3.2 modification processing method, ageing time 12h.
Further, in step 3.2 modification processing method, γ-Al2O3It is in mass ratio 1:1 with ZSM-5.
Further, in step 3.2 modification processing method, maturing temperature is 500 DEG C -600 DEG C.
Prepared by the present invention is a kind of γ-Al2O3@ZSM-5 composite catalyst proposes construction answering based on micro--mesoporous system
The thinking of catalyst is closed, being formed is suitable for B acid-L acid and B acid-L alkali concerted catalysis center, enhances the dissociation under methanol lower temperature
Absorption, to achieve the purpose that greatly improve MTO reactivity, enhancing selectivity of product and extend the ZSM-5 molecular sieve service life.
It is modified when the mixed gas of carrier gas, methanol gas and other unstrpped gases and catalyst of the present invention contact
The B acid and γ-Al of ZSM-5 composite catalyst2O3L acid can form B acid-L acid corrdination centre and B acid-L alkali center, Jin Erzeng
The bottleneck problem of the quick carbon distribution inactivation of absorption dissociation degree and catalyst under strong methanol lower temperature；Another aspect ZSM-5's
Micropore and γ-Al2O3It is mesoporous can form special hierarchical structure, and then weaken the diffusion of molecule, alleviate ZSM-5 molecular sieve carbon distribution
It is formed, extends catalyst life；Meanwhile the special microcellular structure of ZSM-5 is conducive to strengthen the restriction effect of composite catalyst, in turn
Improve the selectivity of target product.γ-Al is made in the present invention2O3@ZSM-5 composite catalyst is applied in methanol producing olefinic hydrocarbons, first sulphur
In the chemical products technique such as alcohol, gasoline, not only has at a lower temperature compared with high reaction activity, also there is the selection of higher product
Property, while ZSM-5 molecular sieve catalytic life can also be greatly improved.
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
Selectivity, while catalytic reaction temperature can be reduced.
Below by specific embodiment, the invention will be further described.
Specific embodiment
Comparative example 1:
Unmodified ZSM-5 catalyst is applied to MTO methanol to olefins 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 and is reacted in alkene processed in MTO, reaction pressure: normal pressure, reaction temperature: 380 DEG C, when heavy
Air speed: 2.0h-1, nitrogen flow rate: 20mLmin-1, water and methanol molar ratio are 2:1, and measuring selectivity of product is 80.88%,
Unmodified catalyst life is 6h.
Comparative example 2:
Unmodified ZSM-5 catalyst is applied to MTO methanol to olefins 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 and is reacted in alkene processed in MTO, reaction pressure: normal pressure, reaction temperature: 400 DEG C, when heavy
Air speed: 2.0h-1, nitrogen flow rate: 20mLmin-1, water and methanol molar ratio are 2:1, and measuring selectivity of product is 81.98%,
Unmodified catalyst life is 7h.
Embodiment 1
A kind of ardealite extracts aluminum for the method for composite catalyst, comprising the following steps:
Step 1: acidleach waste gypsum: after the dilute hydrochloric acid that concentration is 1mol/L is added to drying according to liquid-solid ratio 20mL/g
Waste gypsum powder in, acidleach temperature be 80 DEG C at leaching 1h, centrifugation, take supernatant；
Step 2: separating-purifying aluminium: sodium hydroxide solution being added into the supernatant that step 1 obtains, and carries out solid-liquid point
From, take its supernatant addition concentration for the dilute hydrochloric acid of 1mol/L, until white precipitate all dissolves, generation liquor alumini chloridi, steaming
Concentration, crystallisation by cooling, filtering are sent out, AlCl is obtained3·6H2O
Step 3: the preparation of composite catalyst:
Step 3.1: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=13.2:1, by cetyl
Trimethylammonium bromide CTAB is added to AlCl3·6H2In O solution, stir to dissolution, with peristaltic pump with 5mLmin-1Rate
It is pumped into 3molL-1Precipitating reagent to solution system pH value be 8, continue stir 30min, 80 DEG C of water-bath aging 3h, be cooled to room
Temperature filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, and γ-Al is made in 600 DEG C of roasting 3h2O3Sample；It is described
Precipitating reagent is NH3·H2O。
Step 3.2: with γ-Al obtained in step 3.12O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent.Modification specific method is according to mol ratio Si:Al:TPAOH:H2O=360:1:19:8077, by sodium metaaluminate plus
Enter in deionized water, under continuous stirring, before sequentially adding the tetrapropylammonium hydroxide TPAOH and obtained ZSM-5 of ethyl orthosilicate
Body mixed solution is driven, after aging 10h, by γ-Al2O3Mixed liquor, conversion scale 10ml is added with ZSM-5 1:1 in mass ratio
ZSM-5 precursor liquid can prepare 1g ZSM-5 powder, 180 DEG C of reaction 2h of microwave hydrothermal, and cooling is filtered, washed, and 105~110 DEG C dry
Dry 6h~12h, 450 DEG C of roasting 3h complete modified obtained γ-Al2O3@ZSM-5 composite catalyst.
By γ-Al obtained2O3@ZSM-5 composite catalyst is applied to react in alkene processed in MTO, reaction pressure: normal pressure, instead
Answer temperature: 380 DEG C, weight (hourly) space velocity (WHSV): 2.0h-1, nitrogen flow rate: 20mLmin-1, water and methanol molar ratio are 2:1, measure product
Selectivity is 86.51%, and the modified composite catalyst service life is 8h, and compared with comparative example 1, selectivity of product is improved
5.63%, than unmodified catalyst life 2h.Compared with comparative example 2, selectivity of product improves 4.53%, than
Unmodified catalyst life 1h.
Embodiment 2
A kind of ardealite extracts aluminum for the method for composite catalyst, comprising the following steps:
Step 1: acidleach waste gypsum: after the dilute hydrochloric acid that concentration is 1mol/L is added to drying according to liquid-solid ratio 20mL/g
Waste gypsum powder in, acidleach temperature be 80 DEG C at leaching 1h, centrifugation, take supernatant；
Step 2: separating-purifying aluminium: sodium hydroxide solution being added into the supernatant that step 1 obtains, and carries out solid-liquid point
From, take its supernatant addition concentration for the dilute hydrochloric acid of 1mol/L, until white precipitate all dissolves, generation liquor alumini chloridi, steaming
Concentration, crystallisation by cooling, filtering are sent out, AlCl is obtained3·6H2O solution.
Step 3: the preparation of composite catalyst:
Step 3.1: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=13.2:1, by cetyl
Trimethylammonium bromide CTAB is added to AlCl3·6H2In O solution, stir to dissolution, with peristaltic pump with 5mLmin-1Rate
It is pumped into 3molL-1Precipitating reagent to solution system pH value be 8-9, continue stir 30min, 80 DEG C of water-bath aging 3h, be cooled to room
Temperature filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, and γ-Al is made in 600 DEG C of roasting 3h2O3Sample；It is described
Precipitating reagent is NH3·H2O。
Step 3.2: with γ-Al obtained in step 3.12O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent.Modification specific method is according to mol ratio Si:Al:TPAOH:H2O=360:1:19:8077=360:1:19:
8077, sodium metaaluminate is added in deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and positive silicon
Acetoacetic ester is made ZSM-5 precursor mixed solution, after aging 18h, by γ-Al2O3It is mixed with ZSM-5 1:1 in mass ratio addition
Liquid, conversion scale are that 10ml ZSM-5 precursor liquid can prepare 1g ZSM-5 powder, 180 DEG C of reaction 2h of microwave hydrothermal, cooling, mistake
Filter, washing, 105~110 DEG C of dry 6h~12h, 500 DEG C of roasting 3h complete modified obtained γ-Al2O3@ZSM-5 composite catalyzing
Agent.
By γ-Al obtained2O3@ZSM-5 composite catalyst is applied to react in alkene processed in MTO, reaction pressure: normal pressure, instead
Answer temperature: 380 DEG C, weight (hourly) space velocity (WHSV): 2.0h-1, nitrogen flow rate: 20mLmin-1, water and methanol molar ratio are 2:1, measure product
Selectivity is 86.06%, and the modified composite catalyst service life is 9h, and compared with comparative example 1, selectivity of product is improved
5.18%, than unmodified catalyst life 3h.Compared with comparative example 2, selectivity of product improves 4.08%, than
Unmodified catalyst life 2h.
Embodiment 3
A kind of ardealite extracts aluminum for the method for composite catalyst, comprising the following steps:
Step 1: acidleach waste gypsum: after the dilute hydrochloric acid that concentration is 1mol/L is added to drying according to liquid-solid ratio 20mL/g
Waste gypsum powder in, acidleach temperature be 80 DEG C at leaching 1h, centrifugation, take supernatant；
Step 2: separating-purifying aluminium: sodium hydroxide solution being added into the supernatant that step 1 obtains, and carries out solid-liquid point
From, take its supernatant addition concentration for the dilute hydrochloric acid of 1mol/L, until white precipitate all dissolves, generation liquor alumini chloridi, steaming
Concentration, crystallisation by cooling, filtering are sent out, AlCl is obtained3·6H2O solution.
Step 3: the preparation of composite catalyst:
Step 3.1: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=13.2:1, by cetyl
Trimethylammonium bromide CTAB is added to AlCl3·6H2In O solution, stir to dissolution, with peristaltic pump with 5mLmin-1Rate
It is pumped into 3molL-1Precipitating reagent to solution system pH value be 8-9, continue stir 30min, 80 DEG C of water-bath aging 3h, be cooled to room
Temperature filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, and γ-Al is made in 600 DEG C of roasting 3h2O3Sample；It is described
Precipitating reagent is NaHCO3。
Step 3.2: with γ-Al obtained in step 3.12O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent.Modification specific method is according to mol ratio Si:Al:TPAOH:H2O=360:1:19:8077=360:1:19:
8077, sodium metaaluminate is added in deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and positive silicon
Acetoacetic ester is made ZSM-5 precursor mixed solution, after aging 12h, by γ-Al2O3It is mixed with ZSM-5 1:1 in mass ratio addition
Liquid, conversion scale are that 10ml ZSM-5 precursor liquid can prepare 1g ZSM-5 powder, 180 DEG C of reaction 2h of microwave hydrothermal, cooling, mistake
Filter, washing, 105~110 DEG C of dry 6h~12h, 550 DEG C of roasting 3h complete modified obtained γ-Al2O3@ZSM-5 composite catalyzing
Agent.
By γ-Al obtained2O3@ZSM-5 composite catalyst is applied to react in alkene processed in MTO, reaction pressure: normal pressure, instead
Answer temperature: 380 DEG C, weight (hourly) space velocity (WHSV): 2.0h-1, nitrogen flow rate: 20mLmin-1, water and methanol molar ratio are 2:1, measure product
Selectivity is 90.78%, and the modified composite catalyst service life is 16h, and compared with comparative example 1, selectivity of product is improved
9.90%, than unmodified catalyst life 10h.Compared with comparative example 2, selectivity of product improves 8.80%,
Than unmodified catalyst life 9h.
Embodiment 4
A kind of ardealite extracts aluminum for the method for composite catalyst, comprising the following steps:
Step 1: acidleach waste gypsum: after the dilute hydrochloric acid that concentration is 1mol/L is added to drying according to liquid-solid ratio 20mL/g
Waste gypsum powder in, acidleach temperature be 80 DEG C at leaching 1h, centrifugation, take supernatant；
Step 2: separating-purifying aluminium: sodium hydroxide solution being added into the supernatant that step 1 obtains, and carries out solid-liquid point
From, take its supernatant addition concentration for the dilute hydrochloric acid of 1mol/L, until white precipitate all dissolves, generation liquor alumini chloridi, steaming
Concentration, crystallisation by cooling, filtering are sent out, AlCl is obtained3·6H2O solution.
Step 3: the preparation of composite catalyst:
Step 3.1: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=13.2:1, by cetyl
Trimethylammonium bromide CTAB is added to AlCl3·6H2In O solution, stir to dissolution, with peristaltic pump with 5mLmin-1Rate
It is pumped into 3molL-1Precipitating reagent to solution system pH value be 8-9, continue stir 30min, 80 DEG C of water-bath aging 3h, be cooled to room
Temperature filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, and γ-Al is made in 600 DEG C of roasting 3h2O3Sample；It is described
Precipitating reagent is NH3·H2O。
Step 3.2: with γ-Al obtained in step 3.12O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent.Modification specific method is according to mol ratio Si:Al:TPAOH:H2O=360:1:19:8077=360:1:19:
8077, sodium metaaluminate is added in deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and positive silicon
Acetoacetic ester is made ZSM-5 precursor mixed solution, after aging 12h, by γ-Al2O3It is mixed with ZSM-5 1:1 in mass ratio addition
Liquid, conversion scale are that 10ml ZSM-5 precursor liquid can prepare 1g ZSM-5 powder, 180 DEG C of reaction 2h of microwave hydrothermal, cooling, mistake
Filter, washing, 105~110 DEG C of dry 6h~12h, 600 DEG C of roasting 3h complete modified obtained γ-Al2O3@ZSM-5 composite catalyzing
Agent.
By γ-Al obtained2O3@ZSM-5 composite catalyst is applied to react in alkene processed in MTO, reaction pressure: normal pressure, instead
Answer temperature: 380 DEG C, weight (hourly) space velocity (WHSV): 2.0h-1, nitrogen flow rate: 20mLmin-1, water and methanol molar ratio are 2:1, measure product
Selectivity is 87.75%, and the modified composite catalyst service life is 11h, and compared with comparative example 1, selectivity of product is improved
6.87%, than unmodified catalyst life 5h.Compared with comparative example 2, selectivity of product improves 5.77%, than
Unmodified catalyst life 4h.
Embodiment 5
A kind of ardealite extracts aluminum for the method for composite catalyst, comprising the following steps:
Step 1: acidleach waste gypsum: after the dilute hydrochloric acid that concentration is 1mol/L is added to drying according to liquid-solid ratio 20mL/g
Waste gypsum powder in, acidleach temperature be 80 DEG C at leaching 1h, centrifugation, take supernatant；
Step 2: separating-purifying aluminium: sodium hydroxide solution being added into the supernatant that step 1 obtains, and carries out solid-liquid point
From, take its supernatant addition concentration for the dilute hydrochloric acid of 1mol/L, until white precipitate all dissolves, generation liquor alumini chloridi, steaming
Concentration, crystallisation by cooling, filtering are sent out, AlCl is obtained3·6H2O solution.
Step 3: the preparation of composite catalyst:
Step 3.1: γ-Al2O3Preparation: AlCl is matched by feed molar3·6H2O:CTAB=13.2:1, by cetyl
Trimethylammonium bromide CTAB is added to AlCl3·6H2In O solution, stir to dissolution, with peristaltic pump with 5mLmin-1Rate
It is pumped into 3molL-1Precipitating reagent to solution system pH value be 8-9, continue stir 30min, 80 DEG C of water-bath aging 3h, be cooled to room
Temperature filters, washing, the obtained quasi- boehmite sample of 80 DEG C of dry 6h~12h, and γ-Al is made in 600 DEG C of roasting 3h2O3Sample；It is described
Precipitating reagent is NH3·H2O。
Step 3.2: with γ-Al obtained in step 3.12O3Sample is modified processing to ZSM-5, obtains composite catalyzing
Agent.Modification specific method is according to mol ratio Si:Al:TPAOH:H2O=360:1:19:8077=360:1:19:
8077, sodium metaaluminate is added in deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and positive silicon
Acetoacetic ester is made ZSM-5 precursor mixed solution, after aging 12h, by γ-Al2O3It is mixed with ZSM-5 1:1 in mass ratio addition
Liquid, conversion scale are that 10ml ZSM-5 precursor liquid can prepare 1g ZSM-5 powder, 180 DEG C of reaction 2h of microwave hydrothermal, cooling, mistake
Filter, washing, 105~110 DEG C of dry 6h~12h, 650 DEG C of roasting 3h complete modified obtained γ-Al2O3@ZSM-5 composite catalyzing
Agent.
By γ-Al obtained2O3@ZSM-5 composite catalyst is applied to react in alkene processed in MTO, reaction pressure: normal pressure, instead
Answer temperature: 380 DEG C, weight (hourly) space velocity (WHSV): 2.0h-1, nitrogen flow rate: 20mLmin-1, water and methanol molar ratio are 2:1, measure product
Selectivity is 84.02%, and the modified composite catalyst service life is 10h, and compared with comparative example 1, selectivity of product is improved
3.14%, than unmodified catalyst life 4h.Compared with comparative example 2, selectivity of product improves 2.04%, than
Unmodified catalyst life 3h.
Catalyst of the invention prepares other chemical products, such as methyl mercaptan, ethylene, propylene, gasoline product for methanol
Property has significant improvement, and catalyst life has biggish extension, while can also reduce reaction temperature.
Claims (8)
1. a kind of ardealite extracts aluminum for the method for composite catalyst, which comprises the following steps:
Step 1: acidleach waste gypsum: dilute hydrochloric acid is added in the waste gypsum powder after drying according to liquid-solid ratio 20mL/g, in acid
Soaking temperature is leaching 1h at 80 DEG C, and centrifugation takes supernatant；
Step 2: separating-purifying aluminium: sodium hydroxide solution is added into the supernatant that step 1 obtains, is separated by solid-liquid separation, takes
Dilute hydrochloric acid is added in its supernatant, until white precipitate all dissolves, evaporation and concentration, crystallisation by cooling, filtering obtain AlCl3·6H2O is molten
Liquid；
Step 3: the preparation of composite catalyst:
Step 3.1: 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 prepared in step 23·6H2In 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 3.2: with γ-Al obtained in step 3.12O3Sample is modified processing to ZSM-5, obtains composite catalyst.
2. a kind of ardealite according to claim 1 extracts aluminum for the method for composite catalyst, which is characterized in that step
Rapid one and step 2 in dilute hydrochloric acid concentration be 1mol/L.
3. a kind of ardealite according to claim 1 extracts aluminum for the method for composite catalyst, which is characterized in that step
γ-Al in rapid 3.12O3Sample mesh number is 200 mesh, obtained by being ground up, sieved.
4. a kind of ardealite according to claim 1 extracts aluminum for the method for composite catalyst, which is characterized in that step
Precipitating reagent in rapid 3.1 is NH3·H2O、Na2CO3Or NaHCO3One of.
5. a kind of ardealite according to claim 1 extracts aluminum for the method for composite catalyst, which is characterized in that step
The method of modification in rapid 3.2 are as follows: according to mol ratio Si:Al:TPAOH:H2O=360:1:19:8077, by sodium metaaluminate
It is added in deionized water, under continuous stirring, sequentially adds tetrapropylammonium hydroxide TPAOH and ZSM-5 is made in ethyl orthosilicate
Precursor mixed solution, after aging 8-24h, by γ-Al2O3Mixed liquor, microwave hydrothermal is added with ZSM-5 1-3:1-3 in mass ratio
180 DEG C of reaction 2h, cooling are filtered, washed, 105~110 DEG C of dry 6h~12h, 450 DEG C~650 DEG C roasting 3h, that is, complete to change
Property be made γ-Al2O3@ZSM-5 composite catalyst.
6. a kind of ardealite according to claim 5 extracts aluminum for the method for composite catalyst, which is characterized in that step
In rapid 3.2 modification processing method, ageing time 12h.
7. a kind of ardealite according to claim 5 extracts aluminum for the method for composite catalyst, which is characterized in that step
In rapid 3.2 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 aluminum for the method for composite catalyst, which is characterized in that step
In rapid 3.2 modification processing method, maturing temperature is 500 DEG C -600 DEG C.
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