CN109675548A - A kind of molecular sieve catalyst and preparation method thereof for preparing propylene by dehydrogenating propane - Google Patents

A kind of molecular sieve catalyst and preparation method thereof for preparing propylene by dehydrogenating propane Download PDF

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Publication number
CN109675548A
CN109675548A CN201910055367.6A CN201910055367A CN109675548A CN 109675548 A CN109675548 A CN 109675548A CN 201910055367 A CN201910055367 A CN 201910055367A CN 109675548 A CN109675548 A CN 109675548A
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molecular sieve
catalyst
propane
component
preparing propylene
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朱海波
付静
鲍晓军
袁珮
岳源源
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Fuzhou University
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Fuzhou University
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    • 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
    • B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/42—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 containing iron group metals, noble metals or copper
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    • B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
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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
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract

The molecular sieve catalyst and preparation method thereof that the invention discloses a kind of for preparing propylene by dehydrogenating propane, belongs to field of catalyst preparation.The catalyst is grouped as by two kinds of groups of A and B, and wherein component A is one of metallic element Sn, Ga, Fe, Co, Ni or Zn, and dosage is 1 ~ 9wt% of catalyst total amount, and B component is molecular sieve carrier, and B component dosage is 90 ~ 99wt% of catalyst total amount.The preparation method of the catalyst includes direct hydrothermal synthesis method and infusion process.The present invention prepares high performance alkane dehydrogenating catalyst by dosage, structure and the dispersion degree of control active component, it is simple with preparation process, cheap and nontoxic feature, when being applied to preparing propylene by dehydrogenating propane, it is active it is good, selectivity is high and the features such as stabilization, prepare for the exploitation of alkane dehydrogenating catalyst of new generation and provide new technical solution.

Description

A kind of molecular sieve catalyst and preparation method thereof for preparing propylene by dehydrogenating propane
Technical field
The invention belongs to field of catalyst preparation, and in particular to a kind of molecular sieve catalyst for preparing propylene by dehydrogenating propane And preparation method thereof.
Background technique
Propylene is a kind of extremely important petrochemical industry base stock, and dosage is only second to ethylene, and it is poly- to be widely used in production The basic chemicals such as propylene, acrylonitrile, octyl alconyl and acrylic acid.It is pulled by industries such as real estate, automobile, packaging, textile garments, Propylene it is in strong demand, demand speedup is 1.5 times or so of GDP.It is expected that the five-year whole world speedup 3.8%, domestic 5.2- 7.2%, 1.2 hundred million tons are up to the year two thousand twenty whole world yield and consumption.China propylene market always exists great notch, long The needs in market need to have been met since phase from external a large amount of imports.The quantity and price of China's import propylene in 2017 are innovated again Height, 309.88 ten thousand tons of import propylene, increased by 19.59 ten thousand tons compared with 2016, growth rate 6.75% altogether；Import average price is even more created again New peak reaches 913.6 beauty yuan/ton, is higher by 168.7 beauty yuan/ton compared with import average price in 2016.It can be seen that the propylene market in China The situation of supply and demand anxiety will be faced for a long time, needs to expand the production capacity of propylene to adapt to the great market demand of propylene under the new situation.
In traditional petrochemical industry route, about 61% propylene is produced by naphtha pyrolysis.The production line is remote It is not able to satisfy propylene ever-increasing market demand, the reason of mainly due to the following aspects: (1) the technique main product ethylene, Propylene is joint product, and propylene/ethylene ratio is lower than 0.65 under normal circumstances, results in the limits throughput of propylene；(2) naphtha itself Supply there is also constraints, can not furnish ample material and meet the needs of production of propylene；(3) the low-cost competition work of ethylene Skill --- ethane cracking ethylene production capacity is being expanded rapidly, and naphtha pyrolysis production capacity increases and the utilization of capacity is by serious compression, Therefore naphtha pyrolysis propylene simultaneously sustained production glides in the market.It can be seen that expanding by conventional naphtha cracking technology The potentiality of big propylene yield are extremely limited, need to develop new propane production technology.
The production technology in expansion propylene source has following several: preparing propylene by dehydrogenating propane, methanol-to-olefins (MTO), alkene It is disproportionated propylene processed and kinds of processes combines propylene processed etc..Wherein preparing propylene by dehydrogenating propane route attracts attention in recent years, due to The route raw material is cheap, selectivity of product is high, technique is relatively easy, be increasingly becoming specially produce propylene an economy, can Capable route.It is noted that in recent years in world wide shale gas exploitation technology maturation, provided for dehydrogenating propane technology Sufficient, inexpensive and stable raw material sources, so that the technology has the apparent market competitiveness.
Industrialized catalyst is mainly Pt base and Cr base catalyst to dehydrogenating propane.Due to Cr base catalyst have it is certain Toxicity, practical application space are greatly limited, and are gradually replaced by Pt base catalyst.Though Pt noble metal catalyst It so has excellent performance, but since it is expensive, in addition the catalyst need to be replaced regularly, significantly increase production cost.By This limits their extensive use, needs to develop as it can be seen that the propane dehydrogenation catalyst of two kinds of mainstreams all has some limitations Nontoxic and inexpensive propane dehydrogenation catalyst.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of molecular sieve for preparing propylene by dehydrogenating propane Catalyst and preparation method thereof.When catalyst prepared by the present invention is used for preparing propylene by dehydrogenating propane, selection good with catalytic activity Property high, feature that anti-sintering property is strong and sufficiently stable.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of molecular sieve catalyst for preparing propylene by dehydrogenating propane is grouped as by two kinds of groups of A and B；Wherein component A is gold Belong to one of element S n, Ga, Fe, Co, Ni or Zn, dosage is 1 ~ 9wt% of catalyst total amount, and B component is molecular sieve supported Body, dosage are 90 ~ 99wt% of catalyst total amount.
In component A, the predecessor of Sn includes HSnBu3、SnCl4、Sn(HAC)2、SnCl2·2H2O or HSnPh3In one Kind；The predecessor of Ga includes Ga (NO3)3、GaCl3、Ga2(SO4)3·18H2O or Ga2(SO4)3One of；The predecessor packet of Fe Include Fe (NO3)3·9H2O、(NH4)2Fe(SO4)2·6H2O or FeCl3One of；The predecessor of Co includes Co (CH3COO)2· 4H2O、CoCl2、CoSO4·7H2O or CoBr2One of；The predecessor of Ni includes NiSO4·6H2O or Ni (NO3)2·6H2O One of；The predecessor of Zn includes ZnSO4·7H2O、Zn(NO3)2·6H2O or ZnCl2One of.
The molecular sieve carrier includes ZSM-5 molecular sieve, Y molecular sieve, MCM-22 molecular sieve, beta-molecular sieve or modenite One of.Preferred molecular sieve carrier is ZSM-5 molecular sieve, MCM-22 molecular sieve and beta-molecular sieve.
The preparation method of the molecular sieve catalyst for preparing propylene by dehydrogenating propane, be using direct hydrothermal synthesis method or The molecular sieve catalyst is made in infusion process.
When being prepared using direct hydrothermal synthesis method, synthesis temperature is 70 ~ 250 DEG C, and generated time is 5 ~ 100h.
It is prepared using infusion process, is that B component is carried out to acid processing dealuminzation in advance, it then in proportion will be before component A It drives body to be supported in B component, the molecular sieve catalyst is made in drying, roasting；Acid processing used in acid include nitric acid, Hydrochloric acid or citric acid, treatment temperature are 80 ~ 150 DEG C, and the processing time is 2 ~ 20h；
Or be directly loaded in the presoma of component A in B component in proportion, it is fired and the molecular sieve catalyst is made；Roasting Temperature is 300 ~ 600 DEG C.
The molecular sieve catalyst is applied to preparing propylene by dehydrogenating propane, is to be reacted using fixed bed reactors, instead Answering temperature is 200 DEG C ~ 650 DEG C.
In molecular sieve catalyst of the present invention, using the metallic atom in component A as chain carrier, make it into point Sub- sieve skeleton frame, and Lewis acidity is shown due to the unsaturation of coordination, the preferable catalysis of display is lived in dehydrogenating propane reaction Property.And B component plays a part of to disperse component A as carrier.
Catalyst activity provided by the invention is good, selectivity is high, anti-sintering property is strong and sufficiently stable, is applied to When dehydrogenating propane, higher feed stock conversion and Propylene Selectivity can be obtained.
Compared with prior art, the invention has the benefit that
The present invention in framework of molecular sieve, substantially increases the anti-sintering property of catalyst for metal atom doped.Meanwhile this hair Bright catalyst has high stability, can efficiently convert propylene for propane, delay the deactivation rate of catalyst, improves Service life of catalyst.Compared to mainstream catalyst in the market, catalyst of the invention has nontoxic, inexpensive and uses the longevity Order long feature.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
It is water-soluble for 25% tetrapropylammonium hydroxide (TPAOH) to weigh 27.1g tetraethyl orthosilicate (TEOS), 38.4g mass fraction Liquid, 0.47g SnCl4With 20g H2O is placed in 200mL beaker, stirs 6h at room temperature to hydrolyzing completely, 16g H is added2It will after O Solution is placed in 200mL reaction kettle, filters after reaction 72h under the conditions of 170 DEG C, dries, obtains catalyst after roasting.
In being filled with 1g embodiment 1 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 32%, Propylene Selectivity 90%.
Embodiment 2
By 27.1g tetraethyl orthosilicate (TEOS), 38.4g mass fraction be 25% tetrapropylammonium hydroxide (TPAOH) aqueous solution, 0.46g Ga(NO3)3With 20g H2O is placed in 200mL beaker, stirs 6h at room temperature to hydrolyzing completely, 16g H is added2It will after O Solution is placed in 200mL reaction kettle, filters after reaction 72h under the conditions of 170 DEG C, dries, obtains catalyst after roasting.
In being filled with 1g embodiment 2 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 28%, Propylene Selectivity 89%.
Embodiment 3
By the NaAlO of 0.33g2It is dissolved in 41.4g water, hexa-methylene amine (HMI) 12.5g and Fe is added dropwise under stirring condition (NO3)3·9H2The load capacity of O(Fe is 6wt%), boric acid (H is added after reacting 20min3BO3) 9.8g, continue to drip after stirring 20min Enter JN-40 22.1g, is transferred in polytetrafluoroethylliner liner after gained Primogel aging 2h, reacts 7d under the conditions of 170 DEG C.Instead After answering, cooling, centrifuge separation is washed with water and washs to being in neutrality.By obtained white solid in 100 DEG C of dryings, after be transferred to 600 DEG C of roasting 10h of Muffle furnace, obtain catalyst.
In being filled with 1g embodiment 3 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 30%, Propylene Selectivity 87%.
Embodiment 4
By the NaAlO of 0.33 g2It is dissolved in 41.4g water, hexa-methylene amine (HMI) 12.5g and CoSO is added dropwise under stirring condition4· 7H2The load capacity of O(Co is 6wt%), boric acid (H is added after reacting 20min3BO3) 9.8g, continue to instill JN-40 after stirring 20min It is transferred in polytetrafluoroethylliner liner after 22.1g, gained Primogel aging 2h, reacts 7d under the conditions of 170 DEG C.Reaction terminates Afterwards, cooling, be centrifugated, be washed with water and wash to being in neutrality.By obtained white solid in 100 DEG C of dryings, after be transferred to Muffle furnace 600 DEG C of roasting 10h, obtain catalyst.
In being filled with 1g embodiment 4 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 28%, Propylene Selectivity 87%.
Embodiment 5
By 0.30g NaAlO2、Ni(NO3)2·6H2The load capacity of O(Ni is that 9wt%) and 0.16g NaOH are added to 35mL TEAOH(mass fraction 25%) in aqueous solution, stir to clarify.4.8g white carbon black is added in clear solution, and at room temperature Stir 1h.Mixture is transferred in reaction kettle in 140 DEG C of crystallization 3d.Product is filtered, washed to neutrality, is done in air It is dry, 6h is roasted at 550 DEG C to remove template, obtains catalyst.
In being filled with 1g embodiment 5 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 29%, Propylene Selectivity 92%.
Embodiment 6
By 0.30g NaAlO2、Zn(NO3)2·6H2The load capacity of O(Zn is that 9wt%) and 0.16g NaOH are added to 35mL TEAOH(mass fraction 25%) in aqueous solution, stir to clarify.4.8g white carbon black is added in clear solution, and at room temperature Stir 1h.Mixture is transferred in reaction kettle in 140 DEG C of crystallization 3d.Product is filtered, washed to neutrality, is done in air It is dry, 6h is roasted at 550 DEG C to remove template, obtains catalyst.
In being filled with 1g embodiment 6 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 30%, Propylene Selectivity 91%.
Embodiment 7
6g ZSM-5 molecular sieve is taken, with 120mL 13%HNO3Stir process 12h under the conditions of 120 DEG C of oil baths is filtered, washing, is dried It is dry.Then Fe (the NO that will be prepared3)3·9H2O solution incipient impregnation (load capacity of Fe on processed ZSM-5 molecular sieve For 9wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 7 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 29%, Propylene Selectivity 90%.
Embodiment 8
6g ZSM-5 molecular sieve is taken, with 120mL 13%HNO3Stir process 12h under the conditions of 120 DEG C of oil baths is filtered, washing, is dried It is dry.Then the CoSO that will be prepared4·7H2(load capacity of Co is O solution incipient impregnation on processed ZSM-5 molecular sieve 9wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 8 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 27%, Propylene Selectivity 89%.
Embodiment 9
6g MCM-22 molecular sieve is taken, with 120mL 13%HNO3Stir process 12h under the conditions of 120 DEG C of oil baths, filter, wash, Drying.Then Ni (the NO that will be prepared3)2·6H2(the load of Ni on processed MCM-22 molecular sieve of O solution incipient impregnation Amount is 3wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 9 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 30%, Propylene Selectivity 88%.
Embodiment 10
6g MCM-22 molecular sieve is taken, with 120mL 13%HNO3Stir process 12h under the conditions of 120 DEG C of oil baths, filter, wash, Drying.Then Zn (the NO that will be prepared3)2·6H2(the load of Zn on processed MCM-22 molecular sieve of O solution incipient impregnation Amount is 3wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
It is reaction with propane in being filled with 1g embodiment 10 in the fixed-bed tube reactor of prepared catalyst Object carries out dehydrogenation reaction, and reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, third Alkane conversion ratio is 28%, Propylene Selectivity 87%.
Embodiment 11
6g beta-molecular sieve is taken, with 120mL 13%HNO3Stir process 12h under the conditions of 120 DEG C of oil baths is filtered, washing, drying. Then Ga (the NO that will be prepared3)3Solution incipient impregnation (load capacity of Ga is 6wt%) on processed beta-molecular sieve, at room temperature After reacting 4h, drying, roasting obtains catalyst.
In being filled with 1g embodiment 11 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 31%, Propylene Selectivity 87%.
Embodiment 12
6g beta-molecular sieve is taken, with 120mL 13%HNO3Stir process 12h under the conditions of 120 DEG C of oil baths is filtered, washing, drying.
Then the SnCl that will be prepared2·2H2(load capacity of Sn is O solution incipient impregnation on processed beta-molecular sieve 6wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 12 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 33%, Propylene Selectivity 91%.
Embodiment 13
The ZSM-5 molecular sieve 6g for taking drying, the Ni (NO that will be prepared3)2·6H2O solution incipient impregnation is on ZSM-5 molecular sieve (load capacity of Ni is 6wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 13 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 34%, Propylene Selectivity 87%.
Embodiment 14
The ZSM-5 molecular sieve 6g for taking drying, the Zn (NO that will be prepared3)2·6H2O solution incipient impregnation is on ZSM-5 molecular sieve (load capacity of Zn is 6wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 14 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 33%, Propylene Selectivity 90%.
Embodiment 15
Take the MCM-22 molecular sieve 6g of drying, the Ga (NO that will be prepared3)3Solution incipient impregnation (Ga on MCM-22 molecular sieve Load capacity be 9wt%), at room temperature react 4h after, drying, roasting obtain catalyst.
In being filled with 1g embodiment 15 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 27%, Propylene Selectivity 92%.
Embodiment 16
Take MCM-22 the molecular sieve 6g, the SnCl that will be prepared of drying2·2H2O solution incipient impregnation is on MCM-22 molecular sieve (load capacity of Sn is 9wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 16 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 29%, Propylene Selectivity 90%.
Embodiment 17
The beta-molecular sieve 6g for taking drying, the Fe (NO that will be prepared3)3·9H2(the load of Fe on beta-molecular sieve of O solution incipient impregnation Amount is 3wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 17 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 30%, Propylene Selectivity 88%.
Embodiment 18
Take the beta-molecular sieve 6g of drying, the CoSO that will be prepared4·7H2O solution incipient impregnation (load capacity of Co on beta-molecular sieve For 3wt%), after reacting 4h at room temperature, drying, roasting obtains catalyst.
In being filled with 1g embodiment 18 in the fixed-bed tube reactor of prepared catalyst, using propane as reactant Dehydrogenation reaction is carried out, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, propane Conversion ratio is 34%, Propylene Selectivity 89%.
Comparative example
In the fixed-bed tube reactor of ZSM-5 molecular sieve for being filled with 1g drying, it is anti-that dehydrogenation is carried out using propane as reactant It answers, reaction temperature is 630 DEG C, and reaction pressure is normal pressure, and propane weight (hourly) space velocity (WHSV) is 3.5h-1Under conditions of, conversion of propane is 34%, Propylene Selectivity 38%.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (8)

1. a kind of molecular sieve catalyst for preparing propylene by dehydrogenating propane, it is characterised in that: be grouped as by two kinds of groups of A and B；Wherein Component A is one of metallic element Sn, Ga, Fe, Co, Ni or Zn, and dosage is 1 ~ 9wt% of catalyst total amount, and B component is Molecular sieve carrier, dosage are 90 ~ 99wt% of catalyst total amount.
2. the molecular sieve catalyst according to claim 1 for preparing propylene by dehydrogenating propane, it is characterised in that: in component A, The predecessor of Sn includes HSnBu3、SnCl4、Sn(HAC)2、SnCl2·2H2O or HSnPh3One of；The predecessor of Ga includes Ga(NO3)3、GaCl3、Ga2(SO4)3·18H2O or Ga2(SO4)3One of；The predecessor of Fe includes Fe (NO3)3·9H2O、 (NH4)2Fe(SO4)2·6H2O or FeCl3One of；The predecessor of Co includes Co (CH3COO)2·4H2O、CoCl2、CoSO4· 7H2O or CoBr2One of；The predecessor of Ni includes NiSO4·6H2O or Ni (NO3)2·6H2One of O；The forerunner of Zn Object includes ZnSO4·7H2O、Zn(NO3)2·6H2O or ZnCl2One of.
3. the molecular sieve catalyst according to claim 1 for preparing propylene by dehydrogenating propane, it is characterised in that: the molecule Sieving carrier includes one of ZSM-5 molecular sieve, Y molecular sieve, MCM-22 molecular sieve, beta-molecular sieve or modenite.
4. a kind of preparation method for the molecular sieve catalyst of preparing propylene by dehydrogenating propane as described in claim 1, feature It is: the molecular sieve catalyst is made using direct hydrothermal synthesis method or infusion process.
5. the preparation method of the molecular sieve catalyst according to claim 4 for preparing propylene by dehydrogenating propane, feature exist In: when being prepared using direct hydrothermal synthesis method, synthesis temperature is 70 ~ 250 DEG C, and generated time is 5 ~ 100h.
6. the preparation method of the molecular sieve catalyst according to claim 4 for preparing propylene by dehydrogenating propane, feature exist In: it is prepared using infusion process, is that B component is carried out to acid processing dealuminzation in advance, then in proportion bears the presoma of component A It is loaded in B component, the molecular sieve catalyst is made in drying, roasting；Acid processing used in acid include nitric acid, hydrochloric acid or Citric acid, treatment temperature are 80 ~ 150 DEG C, and the processing time is 2 ~ 20h.
7. the preparation method of the molecular sieve catalyst according to claim 4 for preparing propylene by dehydrogenating propane, feature exist In: when being prepared using infusion process, the presoma of component A is directly loaded in B component, is fired and the molecular sieve is made Catalyst；Maturing temperature is 300 ~ 600 DEG C.
8. a kind of application of molecular sieve catalyst as described in claim 1 in preparing propylene by dehydrogenating propane, it is characterised in that: adopt It is reacted with fixed bed reactors, reaction temperature is 200 DEG C ~ 650 DEG C.
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CN111036260A (en) * 2019-11-11 2020-04-21 中国石油大学(北京) Nitrogen-carbon-doped modified Fe-based catalyst and preparation method and application thereof
CN110801861A (en) * 2019-11-21 2020-02-18 西南化工研究设计院有限公司 Environment-friendly catalyst for preparing propylene by direct dehydrogenation of propane and preparation method thereof
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CN111925271A (en) * 2020-08-17 2020-11-13 湘潭大学 Catalytic decomposition method for preparing propylene by direct dehydrogenation of propane
CN114632539A (en) * 2020-12-16 2022-06-17 中国科学院大连化学物理研究所 Catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation and preparation method and application thereof
CN114797951A (en) * 2021-01-27 2022-07-29 中国科学院大连化学物理研究所 Catalyst for weakening excessive oxidation and enhancing C-H bond activation, preparation and application
CN113441129A (en) * 2021-08-06 2021-09-28 西南化工研究设计院有限公司 Composite metal oxide type alkane dehydrogenation catalyst and preparation method thereof
CN114570417A (en) * 2022-03-23 2022-06-03 清华大学 Catalyst for preparing butene from n-butanol, preparation method of catalyst and method for preparing butene
CN114570415A (en) * 2022-03-28 2022-06-03 福州大学 Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and preparation method thereof
CN114570415B (en) * 2022-03-28 2023-03-14 福州大学 Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and preparation method thereof
CN115487860A (en) * 2022-10-20 2022-12-20 烟台大学 Preparation method and application of composite supported beta molecular sieve catalyst
CN115487860B (en) * 2022-10-20 2024-01-30 烟台大学 Preparation method and application of composite supported beta molecular sieve catalyst
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Application publication date: 20190426