CN106824259B - The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion - Google Patents
The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion Download PDFInfo
- Publication number
- CN106824259B CN106824259B CN201611191439.2A CN201611191439A CN106824259B CN 106824259 B CN106824259 B CN 106824259B CN 201611191439 A CN201611191439 A CN 201611191439A CN 106824259 B CN106824259 B CN 106824259B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- butadiene
- ethyl alcohol
- preparation
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- B01J29/70—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
- B01J29/7615—Zeolite Beta
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/76—Iron group metals or copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of ethyl alcohol convert preparation 1,3- butadiene catalyst with and preparation method thereof, application method.The catalyst is acid treated using H-Beta zeolite molecular sieve as raw material, and the metal active centres of two-component are introduced by infusion process, are Zn and rare earth metal respectively, wherein rare earth metal preferred La, Ce, Pr, Nd, Y, most preferably Y.Preparation method is, mixes acid treated H-Beta zeolite molecular sieve with the nitrate precursors of metal Zn and rare earth metal by metering, dipping is evaporated.The present invention can solve high energy consumption in traditional handicraft, in unstable and production process caused by environmental pollution the problems such as.Catalyst carrier and metal precursor salt of the present invention is all cheap and easy to get, catalyst preparation process is simple, has good stability, it is applied to ethyl alcohol conversion preparation 1 under optimum conditions, there is excellent catalytic activity and selectivity in the technique of 3- butadiene, it is easy to regeneration, the industrial application for converting 1,3-butadiene processed to ethyl alcohol has very big reference.
Description
Technical field
The present invention relates to the bi-component molecular sieve catalysts that a kind of active component is zinc and rare earth metal, which can be with
1,3-butadiene is prepared for catalysis ethanol conversion, while also disclosing the use containing zinc and rare earth metal molecular sieve catalyst
Method.
Background technique
It is well known that 1,3-butadiene is as important Organic Chemicals, industrially, especially China Synthetic Rubber Industry
Extensive application is mainly used for synthesizing polybutadiene rubber (BR), butadiene-styrene rubber (SBR), nitrile rubber (NBR), butylbenzene
The products such as polymer emulsion, styrenic thermoplastic elastomer (SBC) and acrylonitrile-butadiene-styrene (ABS) (ABS) resin, this
It can also be used to produce the Organic chemical products such as adiponitrile, hexamethylene diamine, nylon66 fiber, 1,4-butanediol outside and be used as binder, vapour
Oil additive etc..
The catalyst that catalysis ethanol converts 1,3- butadiene processed has two classes: one kind is oxide catalyst, in patent
A kind of method for preparing butadiene is described in GB331482, wherein using the aluminium oxide catalyst for being mixed with zinc oxide, but fourth
The yield of diene is down to 18%；A kind of solid catalyst is disclosed in patent WO2012/015340Al, contain selected from gold,
Silver-colored or copper metal and the metal oxide selected from magnesium, titanium, zirconium, tantalum or niobium oxide, however this catalyst is but also ethyl alcohol
Conversion ratio it is lower；Trees De Baerdemaeker et al. is in (ACSCatal.2015,5,3393-3397), by dioxy
The bimetallic copper hafnium/zinc hafnium or three metallic copper zirconium zinc/copper hafnium zinc catalyst of SiClx dipping are for catalysis ethanol conversion preparation 1,3-
Butadiene reaction, although the catalyst makes ethanol conversion and butadiene selective increase, stability is not very
It is good.
Another kind of is molecular sieve catalyst, and a kind of method for preparing butadiene is described in CN105451881A, is made
Catalyst is the zeolitic material of the skeleton structure comprising one or more quadrivalent elements, and wherein at least a part is contained in this
The element of skeleton structure is replaced by one or more element X similar shapes, which preferentially selects BEA or MWW zeolite, and X is most preferably
Zirconium and/or tantalum；A kind of ethyl alcohol turn is described in Vitaly L.Sushkevich etc., ACSCatal.2015,5,4833-4836
Change prepares the reaction mechanism of 1,3-butadiene, and the catalyst used is that Beta molecular sieve is acid treated, by synthesizing after two steps
Method synthesizes Ag/Zr-Beta molecular sieve, and the initial selectivity of butadiene is up to 70% or so, but catalyst inactivation is very fast.
Above-mentioned catalyst all has the disadvantage that: oxide catalyst is shape-selective due to not having, so that the conversion of ethyl alcohol
Rate and the selectivity of 1,3-butadiene are lower, and the metal such as tantalum loaded is expensive；Divided as made from two step post synthesis methods
Sub- sieve catalyst, the shape selectivity of molecular sieve makes the initial selectivity of 1,3-butadiene up to 70% or so, but stability is poor, urges
Agent inactivates quickly, and the preparation process of catalyst is relative complex, is not easy to industry's enlarging production.
Summary of the invention
In view of the above deficiencies, the present invention provide a kind of efficient catalysis ethanol conversion prepare 1,3-butadiene catalyst and
Preparation method.In the selection of carrier, according to the shape selectivity of molecular sieve, the H-Beta of three-dimensional twelve-ring cellular structure is chosen
Molecular sieve catalyst is carrier, and the duct suitable size ethyl alcohol of the carrier converts the reaction of 1,3-butadiene processed, is conducive to 1,3-
The generation of butadiene, selectivity up to 70% or so.
Retrieval discovery before being applied, in the prior art, it is undisclosed it is any in relation to use with bimetallic-zinc and rare earth metal
The content of 1,3-butadiene is produced for the catalyst of active component, and proves that this catalyst can be significantly by practice test
The efficiency that ethyl alcohol conversion prepares 1,3-butadiene is improved, stability is good, has filled up the blank of the prior art, improves in production efficiency
Aspect is of great significance.
Technical solution of the present invention is to difficult point existing for the prior art and blank, in the selection of active component, selects
The active component of bimetallic Zn and rare earth metal as the catalysts, so that it is supported on acid using infusion process, treated
On H-Beta molecular sieve, wherein rare earth metal most preferably rare earth metal y.The method for preparing catalyst is simple, and catalyst carrier
All cheap and easy to get with active component Zn and Y, catalyst stability is good, and activity is constant after regeneration, is conducive to carry out industrial applications
Popularization.
The object of the present invention is to provide the catalyst and preparation method thereof that a kind of catalysis ethanol converts 1,3- butadiene processed.This
Invention can solve catalyst preparation process in traditional 1,3-butadiene preparation process is complicated, and expensive and stability is poor etc.
Problem, catalyst dispersity of the invention is more uniform and has excellent stability, and prepares the anti-of 1,3-butadiene in ethyl alcohol
Ying Zhong can obtain the selectivity of 95% ethanol conversion and 70% or so butadiene under conditions of 375 DEG C.In addition, this is urged
The stability of agent is preferable, and the service life can reach 50h, active after regeneration constant to can be recycled.
Catalyst provided by the present invention for preparing 1,3- butadiene is the Zn of component containing bimetallic active and rare earth metal
With acid processing H-Beta molecular sieve, wherein prepared by rare earth metal preferred La, Ce, Pr, Nd, Y, most preferably Y, the catalyst
In the process using H-Beta molecular sieve as raw material, on the one hand, the raw material has good hydrothermal stability, is suitble to ethyl alcohol conversion system 1,
The reaction of 3- butadiene；On the other hand, which has the BEA structure in three-dimensional 12 annulus ducts, has certain shape selectivity, makes
It obtains and is converted in 1,3-butadiene reaction processed in ethyl alcohol, the by-product of some bigger molecules cannot be diffused out from duct, can be protected
Therefore demonstrate,proving higher 1,3-butadiene selectivity has good prospects for commercial application.
The catalyst first has to that H-Beta molecular screen primary powder is placed in concentrated acid by dealumination treatment during the preparation process
In, the regular hour is then handled, molecular sieve whole dealuminzation is made, generates Si-OH nest.Then, by above-mentioned acid treated sample
The presoma inorganic nitrate species of a certain amount of Zn and rare earth metal are introduced by way of dipping.Finally, dipping is evaporated
Said mixture be placed in be connected with air Muffle furnace high temperature roasting, finally obtain the required H- containing Zn and rare earth metal
Beta molecular sieve catalyst, the molecular sieve catalyst, can be on the one hand after dealumination treatment substantially without the acid site Bronsted
Inhibit the dehydration of ethyl alcohol to a certain extent, while delaying the deactivation rate of ethyl alcohol conversion butadiene reacting middle catalyst processed；
On the other hand the introducing of two kinds of active component Zn and rare earth metal can play synergistic effect in the reaction, be conducive to improve catalysis
The activity of agent.
The rare earth metal preferred La, Ce, Pr, Nd, Y, most preferably Y, the load capacity of active component Zn and Y are respectively to urge
The 1-5% and 5-10% of agent quality；The acid processing is concentrated nitric acid；The inorganic precursor nitrate is respectively six water
Zinc nitrate and yttrium nitrate hexahydrate.
The preparation of the catalyst (Zn-Y-Beta catalyst) of 1,3- butadiene is prepared provided by the present invention for ethyl alcohol conversion
Method includes the following steps:
Step 1) is by molar ratio SiO2/Al2O3For 38 ± 1 H-Beta molecular screen primary powder first under conditions of concentrated acid into
Row dealumination treatment.Acid reaction variables are as follows: the H-Beta molecular screen primary powder of 5-10g is placed in the flask with three necks,round bottom of 500mL,
Then 100-200mL concentrated nitric acid is added, is stirred under conditions of condensing reflux in oil bath pan, treatment temperature 80-
120 DEG C, time 10-20h is handled, stirring rate is 500-1000 revs/min；
Step 2): by above-mentioned steps 1) in acid treated that catalyst mixture is transferred in suction funnel, depressurized
It filters, and after filter cake obtained after suction filtration is washed to neutrality, is placed in air dry oven constant temperature 12-24 hours, temperature is
80-120℃；
Step 3): load weighted zinc nitrate hexahydrate according to a certain ratio and yttrium nitrate hexahydrate addition are filled into 40-100mL water
In beaker, be sufficiently stirred, above-mentioned steps 2 be then added) in sample after freeze-day with constant temperature, heated again after stirring 3-6h
To being evaporated, heating temperature is 80-100 DEG C for stirring；
Step 4): by above-mentioned steps 3) in the sample that is evaporated of dipping be put into air dry oven constant temperature 12-24 hours, temperature
It is 80-120 DEG C；It is subsequently placed in Muffle furnace and is roasted under the atmosphere of air, maturing temperature is 500 DEG C -600 DEG C, calcining time
For 3-6h.
The application method for converting the catalyst of 1,3- butadiene processed provided by the present invention for ethyl alcohol includes the following steps:
Step 1) tabletting: the molecular sieve catalyst of yttrium containing zinc that above-mentioned preparation method obtains is placed on tablet press machine and is pressed
Piece sifts out the catalyst 0.3g of 20-40 mesh with sieve, then puts it into the flat-temperature zone of the crystal reaction tube on atmospheric fixed bed
It is reacted after being pre-processed；
Step 2) pretreatment: pre-processing the catalyst in step 1), nitrogen buffer gas when pretreatment, carrier gas stream
Speed is 20-40mL/min, and pretreatment temperature is 450-550 DEG C, pretreatment time 1-2h；
Step 3) reaction: after pretreatment, reactant ethyl alcohol is pumped into double plunger micro-sampling atmospheric fixed bed
In, enter in crystal reaction tube after vaporizer gasifies under the purging of carrier gas, is reacted in catalytic bed, ethyl alcohol flow velocity is
0.5-1mL/h, carrier gas are nitrogen, carrier gas flux 20-40mL/min；
Step 4) analysis: product carries out on-line analysis with gas-chromatography.Wherein, gas-chromatography uses hydrogen flameionization
(FID) detector, column model are the capillary column of Agilent HP-Plot/R (30m × 0.25mm × 0.25 μm), are being reacted
Area normalization method is used in active calculating.
Experiment shows that acidity of catalyst of the present invention is weaker, and structural behaviour is stablized, and catalyst can be used under appropriate conditions
Catalysis ethanol converts in 1,3- butadiene reaction processed.The present invention is in addition to according to the shape selectivity of molecular sieve, selecting in the selection of carrier
The H-Beta molecular sieve catalyst for having taken three-dimensional twelve-ring cellular structure is carrier；Furthermore in the selectivity of active component, choosing
Both active components of bimetallic component as catalyst of metal Zn and rare earth element cheap and easy to get have been taken, it can be effective
Ground catalysis ethanol conversion prepares 1,3-butadiene, and catalyst is more stable, lasts a long time, and catalytic activity is without under obvious after regeneration
Drop；The preparation process of the catalyst is simple, and low in cost, and Catalytic processes are environment friendly and pollution-free, can convert preparation 1 in ethyl alcohol,
Large-scale promotion application in the reaction process of 3- butadiene.
Following example by provided by the present invention for ethyl alcohol conversion prepare 1,3- butadiene react catalyst make into
One step explanation.
Detailed description of the invention
Fig. 1 is the XRD diagram of prepared molecular sieve catalyst.
Fig. 2 is that the SEM of prepared molecular sieve catalyst schemes.
Fig. 3 is that the TEM of prepared molecular sieve catalyst schemes.
Specific embodiment
Further detailed, complete explanation is done to the present invention combined with specific embodiments below.The following description is substantially only
It is merely exemplary and is not intended to the limitation disclosure, application or purposes.
The catalyst for preparing 1,3- butadiene for ethyl alcohol conversion of the invention is Beta points for loading Zn and rare earth metal
Son sieve, rare earth metal most preferably yttrium (Y), specific optional group are divided into Si, O, Zn or Y.The catalyst is during the preparation process with H-
Beta zeolite molecular sieve is raw material.On the one hand, which has good hydrothermal stability, is suitble to ethyl alcohol conversion preparation 1,3- fourth
Diene；On the other hand, which has the BEA structure in three-dimensional 12 annulus ducts, has good shape selectivity, converts in ethyl alcohol
In 1,3-butadiene reaction processed, some macromolecular by-products cannot be diffused out from duct, can guarantee higher butadiene choosing
Therefore selecting property has good prospects for commercial application.
In the preparation, H-Beta molecular sieve first has to by dealumination treatment catalyst of the invention, by by H-Beta points
Son sieve original powder is placed in concentrated acid, and the processing regular hour makes molecular sieve whole dealuminzation, generates Si-OH nest.Then, with above-mentioned acid
Treated, and sample is carrier, the presoma nitrate of metal active constituent Zn and rare earth metal y is introduced by infusion process, finally
The molecular sieve catalyst containing Zn and Y is obtained, on the one hand which reduces after dealumination treatment in Bronsted acid
The heart can inhibit ethanol dehydration；Another aspect non-skeleton metallic zinc and being introduced into for yttrium species convert in butadiene reaction processed in ethyl alcohol
Synergistic effect can be played, the activity for improving catalyst is conducive to.
The load capacity of the metallic zinc and yttrium is respectively the 1-5% and 5-10% of catalyst quality；The acid processing
For concentrated nitric acid；The presoma metal nitrate is zinc nitrate hexahydrate and yttrium nitrate hexahydrate respectively；
The preparation method for converting the catalyst of 1,3- butadiene processed provided by the present invention for ethyl alcohol includes the following steps:
Step 1) is by molar ratio SiO2/Al2O3For 38 ± 1 H-Beta molecular screen primary powder first under conditions of concentrated nitric acid
Carry out dealumination treatment, the acid reaction variables are as follows: the H-Beta molecular screen primary powder of 5-10g is placed in three mouthfuls of the round bottom burnings of 500mL
In bottle, 100-200mL concentrated nitric acid is then added, is stirred under conditions of condensing reflux in oil bath pan, treatment temperature
It is 80-120 DEG C, handles time 10-20h, stirring rate is 500-1000 revs/min；
Step 2): by above-mentioned steps 1) in acid treated that catalyst mixture is transferred in suction funnel, depressurized
It filters, and after filter cake obtained after suction filtration is washed to neutrality, is placed in air dry oven constant temperature 12-24 hours, temperature is
80-120℃；
Step 3): load weighted zinc nitrate hexahydrate according to a certain ratio and yttrium nitrate hexahydrate addition are filled into 40-100mL water
In beaker, be sufficiently stirred, above-mentioned steps 2 be then added) in sample after freeze-day with constant temperature, heated again after stirring 3-6h
To being evaporated, heating temperature is 80-100 DEG C for stirring；
Step 4): by above-mentioned steps 3) in the sample that is evaporated of dipping be put into air dry oven constant temperature 12-24 hours, temperature
It is 80-120 DEG C；It is subsequently placed in Muffle furnace and is roasted under the atmosphere of air, maturing temperature is 500 DEG C -600 DEG C, calcining time
For 3-6h.
Meanwhile the invention also discloses a kind of application method of catalyst for preparing 1,3-butadiene for ethyl alcohol conversion,
Include the following steps:
Step 1) tabletting: the molecular sieve catalyst of yttrium containing zinc that above-mentioned preparation method obtains is placed on tablet press machine and is pressed
Piece sifts out the catalyst 0.3g of 20-40 mesh with sieve, then puts it into the flat-temperature zone of the crystal reaction tube on atmospheric fixed bed
It is reacted after being pre-processed；
Step 2) pretreatment: pre-processing the catalyst in step 1), nitrogen buffer gas when pretreatment, carrier gas stream
Speed is 20-40mL/min, and pretreatment temperature is 450-550 DEG C, pretreatment time 1-2h；
Step 3) reaction: after pretreatment, reactant ethyl alcohol is pumped into double plunger micro-sampling atmospheric fixed bed
In, enter in crystal reaction tube after vaporizer gasifies under the purging of carrier gas, is reacted in catalytic bed, ethyl alcohol flow velocity is
0.5-1mL/h, carrier gas are nitrogen, carrier gas flux 20-40mL/min；
Step 4) analysis: product carries out on-line analysis with gas-chromatography.Wherein, gas-chromatography uses hydrogen flameionization
(FID) detector, column model are the capillary column of Agilent HP-Plot/R (30m × 0.25mm × 0.25 μm), are being reacted
Area normalization method is used in active calculating.
Further detailed, complete explanation is done to the present invention combined with specific embodiments below.
Embodiment 1:
The preparation method of the catalyst of yttrium containing zinc used in the present embodiment (Zn-Y-Beta) includes the following steps:
Step 1) the present embodiment is using H-Beta catalyst as original powder, the silica alumina ratio (SiO of the catalyst2/A2O3) it is 38 ± 1,
Grain size is 100-300nm (see Fig. 2).In addition, XRD is the result shows that the catalyst has good BEA structure, no stray crystal is deposited
At (see Fig. 1).In Zn-Y-Beta preparation process, weigh a certain amount of H-Beta original powder first, under conditions of concentrated nitric acid into
Row processing.Acid reaction variables are as follows: concentrated nitric acid solution is placed in three-necked flask with H-Beta original powder and is mixed, 100 DEG C of oil is placed in
Heating is condensed back stirring 20h in bath.Wherein, the feed ratio of H-Beta molecular screen primary powder and acid solution is 1:20 (g/mL)；
Step 2): will be condensed back in step 1) after the solidliquid mixture after stirring is fully cooled, be added thereto go from
Sub- water is diluted to certain concentration, after decompression filters, resulting filter cake is washed with a large amount of deionized water to neutrality, then will
Freeze-day with constant temperature 12h in its air dry oven for being placed in 100 DEG C；
Step 3) weighs the desired amount of zinc nitrate hexahydrate according to a certain ratio and yttrium nitrate hexahydrate presoma nitrate is placed in burning
In cup, stirred on magnetic stirring apparatus after suitable water is added；
Step 4) weighs a certain amount of solid powder obtained in step 2), is added in the solution in step 3), in magnetic force
After stirring on blender, then heating stirring is to being evaporated on heatable magnetic stirring apparatus, heating temperature 80
DEG C or so；
The sample that dipping is evaporated in step 4) is placed in constant temperature 12h in air dry oven by step 5), and temperature is 80 DEG C；Then
It is put into the Muffle kiln roasting for being connected with air, maturing temperature is 550 DEG C, calcining time 6h.
The TEM chart for preparing resulting catalyst by above method is bright (Fig. 3), the metal Zn and rare earth metal introduced
Y can be distributed in relatively uniformly Beta molecular sieve surface, should the result shows that this patent by introduce Zn and rare earth element y both
Catalyst obtained by active component there is no the structure for destroying molecular sieve, can effectively catalysis ethanol conversion.
Zn-Y-Beta catalyst is used for the application method that ethyl alcohol conversion prepares 1,3-butadiene, is included the following steps:
Step 1) tabletting: it is enterprising that a certain amount of Zn-Y-Beta catalyst that above method preparation obtains is placed on tablet press machine
Row compacting, is then sieved with the sieve of 20-40 mesh, and the catalyst 0.3g of 20-40 mesh is weighed；
Step 2) pretreatment: catalyst load weighted in step 1) is put into the crystal reaction tube on atmospheric fixed bed
Flat-temperature zone, nitrogen buffer gas are pre-processed, nitrogen flow 30mL/min, and pretreatment temperature is 450 DEG C, pretreatment time
For 1h；
Step 3) reaction: the catalyst pre-processed in step 2) is down to reacted temperature, feed ethanol is through twin columns
It fills in micro-sampling pump to enter in crystal reaction tube after vaporizer gasifies under carrier gas nitrogen, be reacted in catalytic bed, it is former
The flow velocity for expecting ethyl alcohol is 0.5mL/h, and the flow of carrier gas nitrogen is 30mL/min, and gasification room temperature is 220 DEG C；
Step 4) product analysis: product carries out on-line analysis with gas-chromatography.Gas-chromatography used is II gas phase of GC7890
Chromatograph, fid detector of arranging in pairs or groups, capillary chromatograph model Agilent HP-PLOT/R.Product is carried out using temperature programming
Separation, heating step are as follows: initial temperature is 60 DEG C, keeps the temperature 2min, is then warming up to 200 DEG C with the rate of 15 DEG C/min, is protected
Warm 6min.The selectivity of the conversion ratio and target product of calculating raw material is sought using area normalization method by chromatographic work station.It chooses anti-
Answering temperature is 350 DEG C, and the reaction time is that the catalytic performance test of 4h the results are shown in Table 1:
1 monometallic active component of table converts the influence of 1,3- Butadiene Extraction Process processed to ethyl alcohol
The catalyst catalytic performance evaluation result of monometallic active component shows: when active component is rare earth metal, ethyl alcohol
Conversion is prepared in the product of 1,3-butadiene, in addition to the product ethylene of ethanol dehydration and ether, only target product 1, and 3- fourth two
Alkene.When other non-rare earth metal active components are catalyzed the reaction, the catalytic activity of Zn-Beta catalyst is relatively excellent, and 1,3-
The yield of butadiene is up to 19.6%.
Embodiment 2
The present embodiment investigates the influence that bimetallic active component prepares butadiene to ethyl alcohol conversion, the i.e. base in embodiment 1
On plinth, selecting Zn or Cu is the first active component, and rare earth metal Ce or Y are second of active component, other reaction conditions are the same as real
It applies described in example 1.Catalytic performance test is shown in Table 2:
2 bimetallic active component of table converts the influence of 1,3- Butadiene Extraction Process processed to ethyl alcohol
The evaluation result of catalyst shows that the first active component Zn is compared with Cu, and Zn has superior performance；Second
Kind active component Y is compared with Ce, and the catalytic performance of rare earth element y is more preferable.Since Zn is amphoteric metal, load is over a molecular sieve
When, it is partial to aobvious alkalinity；And the relative molecular mass of Y is much smaller with respect to for Ce, then when load capacity is identical, the distribution of Y
Wider, active site is more, therefore in the reaction that ethyl alcohol conversion prepares 1,3-butadiene, active component is Zn and rare earth
When metal Y, catalytic activity is more preferable.
Embodiment 3
The present embodiment investigated active component be Zn and Y when, different carriers to catalyst ethyl alcohol convert system 1,3- fourth
The influence of diene technique, the content for choosing active component is 5wt%Zn-5wt%Y, other reaction conditions are the same as described in embodiment 1.
Catalytic performance test is shown in Table 3:
3 carrier of table prepares the influence of 1,3- Butadiene Extraction Process to ethyl alcohol conversion
Catalytic performance test the result shows that: carrier, which converts 1,3-butadiene processed reaction to ethyl alcohol, large effect, with acid
For the structure for Beta molecular sieve that treated there is no being destroyed, the BEA structure in three-dimensional 12 annulus ducts accommodates ethyl alcohol conversion
Prepare 1,3- butadiene.The gas phase SiO of mesoporous MCM-41 molecular sieve and random structure2It is not suitable for ethyl alcohol and converts 1,3- processed
Butadiene.
Embodiment 4
The present embodiment is having selected active component Zn and Y, on the basis of carrier S i-Beta, has investigated different loads amount pair
Ethyl alcohol conversion prepares the influence of 1,3-butadiene performance, other reaction conditions are the same as described in embodiment 1.Catalytic performance test is shown in Table 4:
4 load capacity of table converts the influence of 1,3- Butadiene Extraction Process processed to ethyl alcohol
Catalytic performance test the result shows that: on the basis of total load capacity is fixed as 10wt%, the load capacity of Zn from
When 5wt% is gradually lowered to 1wt%, the conversion of ethyl alcohol take the lead in increase reduce again, when the content of zinc and yttrium be respectively 2wt% and
When 8wt%, the conversion ratio highest of ethyl alcohol can reach 86.2%, and the selectivity of butadiene is also relatively high, can reach
70.6%.Therefore, the Zn and 8wt%Y of 2wt% is optimum load amount, and catalyst 2wt%Zn-8wt%Y-Beta converts ethyl alcohol
Preparation 1,3- butadiene has better catalytic performance.
Embodiment 5
The present embodiment purpose is after selecting suitable load capacity 2wt%Zn-8wt%Y-Beta, investigates temperature to ethyl alcohol
Conversion prepares the influence of 1,3-butadiene, other reaction conditions are the same as described in embodiment 4.Catalytic performance test the results are shown in Table 5:
5 temperature of table prepares the influence of 1,3- Butadiene Extraction Process to ethyl alcohol conversion
Catalytic performance test the result shows that: temperature has apparent influence, as the temperature increases, ethyl alcohol to catalytic performance
Conversion ratio increases, but the yield of 1,3-butadiene is first increased and reduced afterwards, and at 375 DEG C, the yield of 1,3-butadiene is up to
63.5%.Therefore, 375 DEG C are optimal reaction temperature.
Embodiment 6
The present embodiment investigated reaction temperature be 375 DEG C, catalyst loadings be 2wt%Zn-8wt%Y-Beta most
Under the conditions of good, which is applied to ethyl alcohol conversion and prepares the service life in 1,3-butadiene reaction and the catalysis effect after regeneration
Fruit.Catalyst is every to pass through primary recycling, is roasted under the atmosphere of oxygen, and next secondary response is used for, and the flow velocity of oxygen is 30mL/
Min, maturing temperature are 550 DEG C, calcining time 6h.Use after catalyst regeneration the results are shown in Table 6:
Using effect after 6 catalyst regeneration of table
Catalytic performance test the result shows that: under optimum reaction condition, catalyst by regeneration after, catalytic activity is not
Decline.
Specific experiment method and apparatus involved in above-described embodiment unless otherwise specified, be conventional method or according to
The condition of manufacturer's specification suggestion is implemented.Related reagent is commercially available.Mole of H-Beta original powder of the present invention
Than (SiO2/Al2O3) it is 38 ± 1.
Claims (4)
1. a kind of preparation method for the catalyst for preparing 1,3-butadiene for ethyl alcohol conversion, it is characterised in that: the catalyst system
Preparation Method is using H-Beta zeolite molecular sieve as raw material, and acid treated use infusion process introduces two kinds of work of Zn and rare earth metal y
Property center be made, which is characterized in that by metering by the presoma nitre of acid treated H-Beta zeolite molecular sieve and metal Zn and Y
It is sufficiently stirred after hydrochlorate mixing, dipping is evaporated, and is then dried overnight in air dry oven, finally in Muffle kiln roasting；Institute
The load capacity of the activated centre Zn and rare earth metal y that state are respectively the 1%-5% and 5%-10% of catalyst quality；The acid
Processing is sour dealuminzation under normal pressure, and acid used is concentrated nitric acid, and treatment temperature is 80-120 DEG C, and the processing time is 10-20h；Described
Metal precursor nitrate is zinc nitrate hexahydrate and yttrium nitrate hexahydrate.
2. the preparation method of catalyst according to claim 1, which is characterized in that specifically include the following steps:
Step 1) is by molar ratio SiO2/Al2O3It is taken off under conditions of concentrated acid first for 38 ± 1 H-Beta molecular screen primary powder
Aluminium is handled, wherein acid reaction variables are as follows: the H-Beta molecular screen primary powder of 5-10g is placed in the flask with three necks,round bottom of 500mL,
Then 100-200mL concentrated nitric acid is added, is stirred under conditions of condensing reflux in oil bath pan, treatment temperature 80-
120 DEG C, time 10-20h is handled, stirring rate is 500-1000 revs/min；
Step 2): by above-mentioned steps 1) in acid treated that catalyst mixture is transferred in suction funnel, carry out decompression suction filtration,
And after filter cake obtained after suction filtration is washed to neutrality, it is placed in air dry oven constant temperature 12-24 hours, temperature 80-120
℃；
Step 3): load weighted zinc nitrate hexahydrate according to a certain ratio and yttrium nitrate hexahydrate are added to the beaker for filling 40-100mL water
In, be sufficiently stirred, above-mentioned steps 2 be then added) in sample after freeze-day with constant temperature, carry out heating stirring again after stirring 3-6h
To being evaporated, heating temperature is 80-100 DEG C；
Step 4): by above-mentioned steps 3) in the sample that is evaporated of dipping be put into air dry oven constant temperature 12-24 hours, temperature is
80-120℃；It is subsequently placed in Muffle furnace and is roasted under the atmosphere of air, maturing temperature is 500 DEG C -600 DEG C, and calcining time is
3-6h。
3. a kind of catalyst for preparing 1,3-butadiene for ethyl alcohol conversion, which is characterized in that appointed by the claim 1-2
One preparation method is made.
4. a kind of application method for the catalyst for preparing 1,3-butadiene for ethyl alcohol conversion, which is characterized in that including following steps
It is rapid:
Step 1) tabletting: a certain amount of catalyst as claimed in claim 3 is tabletted, sift out the particle of 20-40 mesh
0.3-0.5g, the flat-temperature zone of the crystal reaction tube then put it on atmospheric fixed bed react after being pre-processed；
Step 2) pretreatment: nitrogen pre-processes catalyst in atmospheric fixed bed, carrier gas flux 20- as carrier gas
40mL/min, pretreatment temperature are 450-550 DEG C, pretreatment time 1-2h；
Step 3) reaction: feed ethanol is brought into fixed bed through double plunger micro-sampling pump, through vaporizer under the purging of carrier gas
Gasification enters in the crystal reaction tube in fixed bed, is reacted in catalytic bed to get product is arrived, wherein feed ethanol flow velocity is
0.5-1mL/h, carrier gas are nitrogen, flow 20-40mL/min；Reaction condition is 300-400 DEG C, reaction time 1-50h；
Step 4) product carries out on-line analysis with gas-chromatography.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611191439.2A CN106824259B (en) | 2016-12-21 | 2016-12-21 | The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611191439.2A CN106824259B (en) | 2016-12-21 | 2016-12-21 | The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106824259A CN106824259A (en) | 2017-06-13 |
| CN106824259B true CN106824259B (en) | 2019-07-12 |
Family
ID=59135236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611191439.2A Active CN106824259B (en) | 2016-12-21 | 2016-12-21 | The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106824259B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3689452A4 (en) * | 2017-09-27 | 2021-06-30 | Sekisui Chemical Co., Ltd. | Catalyst, device for manufacturing conjugated diene, and method for manufacturing conjugated diene |
| CN109833904B (en) * | 2017-11-29 | 2020-08-11 | 中国科学院大连化学物理研究所 | Acid-base bifunctional catalyst, preparation method thereof and application thereof in ethanol conversion reaction |
| CN108097300B (en) * | 2017-12-15 | 2020-06-05 | 南开大学 | Catalyst for preparing isobutene by acetic acid conversion and preparation method thereof |
| CN113181958A (en) * | 2021-04-14 | 2021-07-30 | 中山大学 | Catalyst and preparation method and application thereof |
| CN113289670B (en) * | 2021-04-14 | 2022-11-08 | 中山大学 | Catalyst for preparing 1,3-butadiene and preparation method thereof |
| CN113600231B (en) * | 2021-08-06 | 2023-01-20 | 西北大学 | Preparation method of catalyst for preparing 1, 3-butadiene by ethanol two-step method |
| CN113663721B (en) * | 2021-09-07 | 2023-10-17 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of catalyst for preparing 1, 3-butadiene from ethanol |
| CN113830779A (en) * | 2021-10-25 | 2021-12-24 | 江西师范大学 | Preparation method and application of cobalt-containing Beta molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920527A (en) * | 2014-04-24 | 2014-07-16 | 南开大学 | Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof |
| CN105451881A (en) * | 2013-06-13 | 2016-03-30 | 巴斯夫欧洲公司 | Process for the preparation of butadiene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016066869A1 (en) * | 2014-10-30 | 2016-05-06 | Abengoa Research, S.L. | Microporous catalyst with selective encapsulation of metal oxides, used to produce butadiene precursors |
-
2016
- 2016-12-21 CN CN201611191439.2A patent/CN106824259B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105451881A (en) * | 2013-06-13 | 2016-03-30 | 巴斯夫欧洲公司 | Process for the preparation of butadiene |
| CN103920527A (en) * | 2014-04-24 | 2014-07-16 | 南开大学 | Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Ag-Promoted ZrBEA Zeolites Obtained by Post-Synthetic Modification for Conversion of Ethanol to Butadiene";Vitaly L. Sushkevich et al;《ChemSusChem》;20160823;第9卷;第2216-2225页 |
| "Bimetallic Zn and Hf on Silica Catalysts for the Conversion of Ethanol to 1,3-Butadiene";Trees De Baerdemaeker et al;《ACS Catal.》;20150424;第5卷;第3393-3397页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106824259A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106824259B (en) | The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion | |
| CN106423263B (en) | A kind of synthesis of the catalyst and low-carbon alkene of hydrogenation of carbon dioxide producing light olefins | |
| CN106345514B (en) | A kind of catalyst and preparation method thereof of one step of synthesis gas conversion producing light olefins | |
| CN106365995B (en) | A kind of production method of methyl acetate | |
| CN105983435B (en) | A kind of isomerization of butene catalyst and its preparation method and application | |
| CN103008001B (en) | Fischer-Tropsch synthesis catalyst comprising composite molecular sieve, and preparation method and application thereof | |
| CN105498839B (en) | A kind of heterogeneous catalysis and preparation method thereof of catalysis asymmetric Aldol reaction | |
| CN109894144B (en) | Synthesis method of 1, 3-butadiene and preparation method of catalyst thereof | |
| CN104148107A (en) | Catalyst for preparing diesel fractions by one-step conversion of synthesisgas and preparation method of catalyst | |
| CN109503388A (en) | The method of coproduction cyclohexylamine and dicyclohexyl amine and catalyst system for this method | |
| CN103007982A (en) | Fischer-Tropsch synthesis catalyst comprising zeolite molecular sieve, and preparation method and application thereof | |
| CN106622338B (en) | Catalyst and application thereof for the reaction of methylbenzene methanol side chain alkylation | |
| CN106622339B (en) | Catalyst and its application for the reaction of methylbenzene methanol side chain alkylation | |
| CN111054326B (en) | Supported catalyst, preparation method thereof and application of supported catalyst in catalyzing synthesis of indole from ethylene glycol and aniline | |
| CN109395772A (en) | A kind of isomerization catalyst and its preparation method and application | |
| CN102211036A (en) | Modified molecular sieve catalyst, and precursor and preparation method thereof | |
| CN108144642B (en) | A kind of oil hydrogenation HC fuel catalyst and preparation and application | |
| CN103861633B (en) | A kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL | |
| CN114349973B (en) | Lanthanum-manganese bimetal quasi-organic framework material and preparation method and application thereof | |
| CN106890669A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN102816054B (en) | Environment-friendly method for preparing adipic acid by catalytic oxidation | |
| CN105498829B (en) | A kind of aromatization of methanol catalyst and its preparation method and application | |
| CN107233886A (en) | For preparing α, the cobalt-base catalyst and preparation method and purposes of β unsaturated alcohols | |
| CN107008489A (en) | Molecular sieve carried catalytic component based on vanadium for lignin hydrodepolymerization and preparation method thereof | |
| CN107983326A (en) | A kind of preparation method of hydrogenation catalyst shaping carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |