CN107899607A - A kind of modified beta molecular sieve and its preparation method and application - Google Patents
A kind of modified beta molecular sieve and its preparation method and application Download PDFInfo
- Publication number
- CN107899607A CN107899607A CN201711145548.5A CN201711145548A CN107899607A CN 107899607 A CN107899607 A CN 107899607A CN 201711145548 A CN201711145548 A CN 201711145548A CN 107899607 A CN107899607 A CN 107899607A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- beta
- metallic element
- preparation
- catalyst
- 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.)
- Pending
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
- B01J29/72—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
-
- 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
- B01J29/7007—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
- B01J29/7049—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of modified beta molecular sieve and its preparation method and application.The catalyst is the described method includes using beta-molecular sieve as matrix, and using metallic element as modifying agent, using the solution of metallic element soluble salt, the modified beta molecular sieve is prepared using ion-exchange；One or more mixing of the metallic element in Cu, Al, Zn, Fe and Sn；Mass content of the metallic element in obtained modified beta molecular sieve is 0.5 4%.The catalyst preparation process is simple, cost is relatively low, and its esterification activity is higher, lasts a long time, overcome etching apparatus, poor selectivity, esterification yied when using the concentrated sulfuric acid as catalyst it is low, pollution environment, and using the shortcomings of ion exchange resin preparation process is complicated, cost is higher, non-refractory, there is good prospects for commercial application.
Description
Technical field
The present invention relates to chemical field, specifically, the present invention relates to a kind of modified beta molecular sieve and preparation method thereof and answers
With.
Background technology
Sec-butyl acetate is one of four kinds of isomers of butyl acetate, it is a kind of liquid that is colourless, inflammable, having fruit flavor
Body, it is not soluble in water, can be miscible with ethanol, ether.Sec-butyl acetate is widely used, suitable for nitrocellulose, medicine, coating, height
In the industry such as shelves paint, artificial leather, spices, ink and plastics；Methyl tertiary butyl ether(MTBE) can also be substituted at the same time, is added as gasoline
Add agent.
At present, the domestic prevailing method for preparing sec-butyl acetate is acetic acid and sec-butyl alcohol direct esterification.
In this method, the selection of catalyst is even more important, and most traditional catalyst is the concentrated sulfuric acid.CN1844076A disclose it is a kind of with
The concentrated sulfuric acid is catalyst, with the method for reaction rectification method production butyl acetate.Although concentrated sulfuric acid catalytic activity is higher, price is low
It is honest and clean, but as the catalyst of esterification, there is very big deficiency：First, during the reaction, due to being esterified, being etherified and aoxidizing
Occur at the same time Deng reaction, cause accessory substance more, increase the difficulty of raw materials recovery and product purification；Secondly, the concentrated sulfuric acid cannot
Recycle, pollute environment；Again, concentrated sulfuric acid etching apparatus, increases industrial production cost.Therefore, searching can substitute dense sulphur
The novel ester catalysts of acid have become the hot spot of current research and exploitation.
CN1323655 discloses a kind of SO prepared with co-precipitation-infusion process4 2-/Fe2O3-ZrO2-SiO2Superacid catalysis
Agent is catalyzed the reaction of acetic acid and butanol, and the yield of butyl acetate reaches 93.3%, and selectivity is 96.0%.Since super acids are anti-
During answering, especially under the conditions of having existing for water, SO4 2-Easily it is lost in, causes catalyst easy in inactivation, catalyst uses the longevity
Order it is short, and inactivate after catalyst be difficult to regenerate.
CN1136470A discloses a kind of catalyst being made of cation exchange resin and sulfate, and wherein cation is handed over
It is 80~95% to change resin proportion, and sulfate proportion is 5~20%.The catalyst is used to be catalyzed acetic acid and ethanol
Esterification, the yield of ethyl acetate is 99.7%.The catalyst stills need to use the concentrated sulfuric acid in process of production.
CN100503043C discloses a kind of alkyl pyrrolidone group containing N-Acid ion liquid catalyst,
For being catalyzed the esterification of acetic acid and butanol.When reaction temperature is 110 DEG C, after reacting 2h, the conversion ratio of acetic acid is 100%,
The selectivity of butyl acetate is 100%.The catalyst is suitable for intermittent reaction, is unfavorable for continuous production.
CN101574667B discloses a kind of heteropoly acid and organic phosphine catalyst and its application in the esterification reaction.It is first
Organic phosphine and alkyl sultone are first reacted to the season phosphine type inner salt of generation side chain containing alkyl sulfonic acid in organic solvent, then will
Season phosphine type inner salt and 12- phosphotungstic acids, 12- silico-tungstic acids or 12- phosphomolybdic acids difference wiring solution-forming, be stirred the organic heteropoly acid of generation
Salt.The esterification of the catalyst acetic acid and butanol, butyl acetate yield are selectively up to 97.2%, butyl acetate
100%.But the reaction is homogeneous reaction, catalyst is not easily recycled, it is difficult to is industrialized.
CN105820052A discloses a kind of method using Supported on Zeolite catalyst preparation butyl acetate.This method will
Butanol, acetic acid and water three are 2~5 according to volume:1:3 ratio is added in reaction kettle of the esterification, and puts into and account for reaction system
Volume toatl proportion is 5~30% Supported on Zeolite catalyst, reacts 15~30min under conditions of being 80~115 DEG C in temperature
After condense, rectifying recycling, up to more than 98%, butyl acetate yield is more than 99.5% for the conversion ratio of acetic acid.In the catalyst
Molecular sieve component is ZSM-5 or MCM-22, and immobilized catalytic component is 12 phosphotungstic acids, 12 silico-tungstic acids and 12 phosphomolybdate
In one kind or their compositions.
At present, disclosed in patent the novel solid acid esterification catalyst of the concentrated sulfuric acid can be replaced to have ion exchange resin, miscellaneous more
Acid, solid super-strong acid, metal sulfate and molecular sieve.But be not easy to regenerate after ion exchange resin non-refractory, inactivation, it is miscellaneous
The active component of polyacid, metal sulfate and solid super-strong acid is easy to run off, the molecular sieve catalyst reported or containing molecular sieve
The preparation process of composite catalyst is complicated, of high cost.The present invention prepares catalyst using simple method to beta-molecular sieve modification
For the synthesis of sec-butyl acetate, solve it is existing prepare sec-butyl acetate catalytic erosion equipment, cost is higher, activity is low and
The problems such as sec-butyl acetate product purity is not high.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of modified beta molecular sieve.
The modified beta molecular sieve obtained another object of the present invention is to provide the preparation method.
It is still another object of the present invention to provide a kind of lactate synthesis method of acetic acid and sec-butyl alcohol.The present invention is for existing
Acetic acid and sec-butyl alcohol catalyst for esterification reaction etching apparatus, cost is higher, activity is low, poor selectivity, esterification yied it is low with
And pollution environment the deficiencies of, there is provided a kind of preparation process is simple, cost is relatively low, esterification it is active it is higher, last a long time it is green
Color catalyst and preparation method, with the substitution commercial concentrated sulfuric acid and ion-exchange resin catalyst.
In order to achieve the above object, on the one hand, the present invention provides a kind of preparation method of modified beta molecular sieve, wherein, the side
Method is included using beta-molecular sieve as matrix, and using metallic element as modifying agent, ion exchange is used using the solution of metallic element soluble salt
The modified beta molecular sieve is prepared in method；The metallic element is one or more mixed in Cu, Al, Zn, Fe and Sn
Close；Mass content of the metallic element in obtained modified beta molecular sieve is 0.5-4%.
Some specific embodiments according to the present invention, wherein, matter of the metallic element in obtained modified beta molecular sieve
Amount content is 0.5-4%.
Some specific embodiments according to the present invention, wherein, the soluble salt of the metallic element is selected from the metallic element
Chloride, nitrate, one or more mixing in acetate and phosphate.
Some specific embodiments according to the present invention, wherein, solution of the metal soluble salt in the metal soluble salt
In molar concentration be 0.1-1.0mol/L.
Some specific embodiments according to the present invention, wherein, the solution of the metal soluble salt and the ratio of matrix are 5:1
(mL/g)。
Some specific embodiments according to the present invention, wherein, solvent in the solution of the metal soluble salt be selected from water or
Organic solvent.
Some specific embodiments according to the present invention, wherein, the organic solvent is the alcohol that carbon number is 1-4.
Some specific embodiments according to the present invention, wherein, the beta-molecular sieve is Hydrogen beta-molecular sieve.
Some specific embodiments according to the present invention, wherein, the beta-molecular sieve is the Hydrogen beta molecule that silica alumina ratio is 20-60
Sieve.
Some specific embodiments according to the present invention, wherein, the beta-molecular sieve is the Hydrogen beta molecule that silica alumina ratio is 20-40
Sieve.
Some specific embodiments according to the present invention, wherein, the described method includes can by beta-molecular sieve and the metallic element
The step of solution mixing of dissolved salt, stirring 4-10h.
Some specific embodiments according to the present invention, wherein, the described method includes can by beta-molecular sieve and the metallic element
The solution mixing of dissolved salt, stirs 4-10h, is then washed with water, is dried to obtain the modified beta molecular sieve.
Some specific embodiments according to the present invention, wherein, the step of the method further includes roasting, then obtain described
Modified beta molecular sieve.
Some specific embodiments according to the present invention, wherein, the temperature of roasting is 400-600 DEG C.
Some specific embodiments according to the present invention, wherein, the time of roasting is 3-10h.
Some specific embodiments according to the present invention, wherein, the method specifically includes：Configure 0.1~1.0mol/L's
Metal chloride, nitrate, acetate or phosphate solution, solvent selection water or organic solvent, organic solvent can be C2~C4
Alcohol；Then by 20~40g beta-molecular sieves and the certain density metal chlorides of 100~200g or nitrate solution in stirring shape
3~10h of ion-exchange reactions is carried out under state；With water or ethanol filtering and washing reaction product, then at 80~120 DEG C in baking oven
Dry 8~16h；It is finally 0~10h in 400~600 DEG C of roasting times in Muffle furnace, divides after cooling up to metal-modified β
Son sieve.
Some specific embodiments according to the present invention, wherein, the method is further included modified beta molecular sieve compression molding,
And it is sized to the step of 20~40 mesh.
On the other hand, present invention also offers the modified beta molecular sieve that the preparation method described in any one of the present invention obtains.
Some specific embodiments according to the present invention, wherein, the specific surface area of the modified beta molecular sieve for 515~
534m2/ g, pore volume are 0.36~0.38cm3/g。
Relative to unmodified commercial Hydrogen beta-molecular sieve following change occurs for the Acidity of the modified beta molecular sieve of the present invention：
The acid strength of strong acid reduces, and the acid amount increase in the Lewis acid sites of weak acid, the acid amount in the Lewis acid sites of strong acid reduces (such as
Shown in table 1).
Another further aspect, present invention also offers a kind of lactate synthesis method of acetic acid and sec-butyl alcohol, wherein, the synthesis side
Method includes being reacted as catalyst using the modified beta molecular sieve described in claim 7.
Some specific embodiments according to the present invention, wherein, the reaction is carried out in fixed bed reactors.
Some specific embodiments according to the present invention, wherein, the fixed bed reactors are micro fixed-bed reactor
(micro fixed-bed reactor of 10mL).
Some specific embodiments according to the present invention, wherein, the condition of the reaction includes：Reaction temperature is 100-140
DEG C, reaction pressure 0.5-2.5MPa.
Some specific embodiments according to the present invention, wherein, the condition of the reaction includes：Mole of sec-butyl alcohol and acetic acid
Than for (1:1)-(4:1), weight (hourly) space velocity (WHSV) 0.5-2h-1。
In conclusion the present invention provides a kind of modified beta molecular sieve and its preparation method and application.Prepared by the present invention changes
Property beta-molecular sieve had the following advantages that relative to unmodified commercial Hydrogen beta-molecular sieve：The acid strength of strong acid reduces, weak acid
The acid amount increase in Lewis acid sites, the acid amount in the Lewis acid sites of strong acid reduce (as shown in table 1)；And in carried metal amount base
The relatively low metallic element of price, catalyst cost reduction are largely employed in the case that this is constant；Without equipment corrosion problem.This
Invention carries out metal-modified beta-molecular sieve catalyst in the esterification of acetic acid and sec-butyl alcohol, the conversion per pass and second of acetic acid
The selectivity of the secondary butyl ester of acid can respectively reach 72% and 93%.
Brief description of the drawings
Fig. 1 is the schematic diagram of the fixed bed reactors of synthetic example of the present invention；Wherein drawing reference numeral is：
1st, 2,7,15 be ball valve；3 be pressure reducing valve；4th, 14 be gas flowmeter；5 be head tank；6 be micro pump；8 be preheating
Device；9 be reactor；10 be condenser；11 be high pressure knockout drum；12 be low pressure separation pot；13 be counterbalance valve；16 receive for product
Tank.
Embodiment
Below by way of the specific embodiment implementation process that the present invention will be described in detail and the beneficial effect produced, it is intended to which help is read
Reader more fully understand the present invention essence and feature, not as to this case can practical range restriction.
The esterification of acetic acid and sec-butyl alcohol carries out in miniature (10mL) fixed bed reactors, its flow such as Fig. 1 institutes
Show.Fixed bed reactors mainly include three sampling system, reaction system and piece-rate system parts.Sampling system include gas circuit and
Enter reactor after nitrogen is measured by mass flowmenter in fluid path two parts, wherein gas circuit, and acetic acid and sec-butyl alcohol in fluid path
Then by entering reactor after micro-measurement pump-metered.Reactor is outside diameter 19.0mm, internal diameter 14.0mm, the 316L of length 650mm
Stainless steel tube.Acetic acid and sec-butyl alcohol enter in reactor react after enter piece-rate system, reaction product is condensed laggard
Enter product collector.
Embodiment 1
20g beta-molecular sieves (silica alumina ratio 21) are added to the Cu (NO of 100mL 0.2mol/L3)2Aqueous solution, at room temperature
6h is stirred, reaction product is filtered with deionized water, dry, 450 DEG C of roasting 4h in Muffle furnace, through compression molding and are sized to 20
~40 mesh, that is, obtain the beta-molecular sieve catalyst of Cu modifications, spare.Wherein quality of the Cu elements in obtained molecular sieve contains
Measure as 2.5%.
The beta-molecular sieve catalyst being modified with the Cu of the above-mentioned preparations of 3g, the esterification for carrying out catalysis acetic acid and sec-butyl alcohol are commented
Valency.By acetic acid and sec-butyl alcohol according to molar ratio 1:2 are passed through the 10mL fixed bed reactors of self assembly, reaction pressure 1.5MPa,
Weight (hourly) space velocity (WHSV) is 1.0h-1, reaction temperature is 120 DEG C.The result shows that：After reaction carries out 50h, the conversion ratio of acetic acid is 62.52%,
The selectivity of sec-butyl acetate is 86.89%.
Embodiment 2
30g beta-molecular sieves (silica alumina ratio 21) are added to the Al (NO of 150mL 0.4mol/L3)3Aqueous solution, at room temperature
6h is stirred, reaction product is filtered with deionized water, it is dry, through compression molding and 20~40 mesh are sized to, that is, obtain the β of Al modifications
Molecular sieve catalyst, it is spare.Wherein Al elements (including intrinsic Al species and additional Al sources in molecular sieve) are obtained
Quality total content in molecular sieve is 3.8%.Its Acidity is listed in Table 1 below.
The beta-molecular sieve catalyst being modified with the Al of the above-mentioned preparations of 3g, the esterification for carrying out catalysis acetic acid and sec-butyl alcohol are commented
Valency.By acetic acid and sec-butyl alcohol according to molar ratio 1:4 are passed through the fixed bed reactors of self assembly, reaction pressure 0.5MPa, when heavy
Air speed is 1.0h-1, reaction temperature is 110 DEG C.The result shows that：After reaction carries out 50h, the conversion ratio of acetic acid is 72.00%, acetic acid
The selectivity of secondary butyl ester is 86.54%.
Embodiment 3
20g beta-molecular sieves (silica alumina ratio 26) are added to the Zn (NO of 100mL 0.4mol/L3)2Aqueous solution, at room temperature
4h is stirred, reaction product is filtered with deionized water, dry, 500 DEG C of roasting 6h in Muffle furnace, through compression molding and are sized to 20
~40 mesh, that is, obtain the beta-molecular sieve catalyst of Zn modifications, spare.Wherein quality of the metallic element in obtained molecular sieve
Content is 1.5%.
The beta-molecular sieve catalyst being modified with the Zn of the above-mentioned preparations of 3g, the esterification for carrying out catalysis acetic acid and sec-butyl alcohol are commented
Valency.By acetic acid and sec-butyl alcohol according to molar ratio 1:2 are passed through the fixed bed reactors of self assembly, reaction pressure 2.5MPa, when heavy
Air speed is 0.8h-1, reaction temperature is 120 DEG C.The result shows that：After reaction carries out 50h, the conversion ratio of acetic acid is 65.46%, acetic acid
The selectivity of secondary butyl ester is 91.82%.
Embodiment 4
30g beta-molecular sieves (silica alumina ratio 26) are added to the Fe (NO of 150mL 0.4mol/L3)3Aqueous solution, at room temperature
6h is stirred, reaction product is filtered with deionized water, it is dry, through compression molding and 20~40 mesh are sized to, that is, obtain the β of Fe modifications
Molecular sieve catalyst, it is spare.Wherein mass content of the metallic element in obtained molecular sieve is 2.5%.Its Acidity arranges
In table 1.
The beta-molecular sieve catalyst being modified with the Fe of the above-mentioned preparations of 3g, the esterification for carrying out catalysis acetic acid and sec-butyl alcohol are commented
Valency.By acetic acid and sec-butyl alcohol according to molar ratio 1:3 are passed through the fixed bed reactors of self assembly, reaction pressure 1.5MPa, when heavy
Air speed is 0.8h-1, reaction temperature is 120 DEG C.The result shows that：After reaction carries out 50h, the conversion ratio of acetic acid is 67.31%, acetic acid
The selectivity of secondary butyl ester is 92.50%.
Embodiment 5
20g beta-molecular sieves (silica alumina ratio 40) are added to the SnCl of 100mL 0.4mol/L2Ethanol solution, at room temperature
8h is stirred, reaction product is filtered with ethanol, dry, 520 DEG C of roasting 4h in Muffle furnace, through compression molding and are sized to 20~40
Mesh, that is, obtain the beta-molecular sieve catalyst of Sn modifications, spare.Wherein mass content of the metallic element in obtained molecular sieve
For 0.7%.
The beta-molecular sieve catalyst being modified with the Sn of the above-mentioned preparations of 3g, the esterification for carrying out catalysis acetic acid and sec-butyl alcohol are commented
Valency.By acetic acid and sec-butyl alcohol according to molar ratio 1:2 are passed through the fixed bed reactors of self assembly, reaction pressure 2.0MPa, when heavy
Air speed is 0.5h-1, reaction temperature is 110 DEG C.The result shows that：After reaction carries out 50h, the conversion ratio of acetic acid is 71.42%, acetic acid
The selectivity of secondary butyl ester is 78.30%.
Embodiment 6
30g beta-molecular sieves (silica alumina ratio 26) are added to the FeCl of 150mL 0.4mol/L3Aqueous solution, is stirred at room temperature
6h is mixed, reaction product is filtered with deionized water, it is dry, through compression molding and 20~40 mesh are sized to, that is, obtain β points of Fe modifications
Sub- sieve catalyst, it is spare.Wherein mass content of the metallic element in obtained molecular sieve is 2.7%.Its Acidity is listed in
In table 1.
The beta-molecular sieve catalyst being modified with the Fe of the above-mentioned preparations of 3g, the esterification for carrying out catalysis acetic acid and sec-butyl alcohol are commented
Valency.By acetic acid and sec-butyl alcohol according to molar ratio 1:2 are passed through the fixed bed reactors of self assembly, reaction pressure 1.5MPa, when heavy
Air speed is 0.8h-1, reaction temperature is 140 DEG C.The result shows that：After reaction carries out 50h, the conversion ratio of acetic acid is 72.15%, acetic acid
The selectivity of secondary butyl ester is 89.94%.
Embodiment 7
20g beta-molecular sieves (silica alumina ratio 26) are added to the FeCl of 100mL 0.2mol/L3Ethanol solution, at room temperature
4h is stirred, reaction product is filtered with deionized water, dry, 520 DEG C of roasting 4h in Muffle furnace, through compression molding and are sized to 20
~40 mesh, that is, obtain the beta-molecular sieve catalyst of Fe modifications, spare.Wherein quality of the metallic element in obtained molecular sieve
Content is 2.2%.
The beta-molecular sieve catalyst being modified with the Fe of the above-mentioned preparations of 3g, the esterification for carrying out catalysis acetic acid and sec-butyl alcohol are commented
Valency.By acetic acid and sec-butyl alcohol according to molar ratio 1:2 are passed through the fixed bed reactors of self assembly, reaction pressure 1.5MPa, when heavy
Air speed is 1.0h-1, reaction temperature is 120 DEG C.The result shows that：After reaction carries out 50h, the conversion ratio of acetic acid is 71.25%, acetic acid
The selectivity of secondary butyl ester is 90.03%.
Embodiment 8
The beta-molecular sieve catalyst that the Fe prepared in embodiment 7 is modified carries out acetic acid and the long period esterification of sec-butyl alcohol is anti-
It should evaluate, the molar ratio of acetic acid and sec-butyl alcohol is 1:2, reaction temperature is 110 DEG C, reaction pressure 2.0MPa, and weight (hourly) space velocity (WHSV) is
0.8h-1.The result shows that：After reaction carries out 180h, the conversion ratio of acetic acid remains to reach 70.1%, and the selectivity of sec-butyl acetate is
91.0%.
Comparative example 1
By Hydrogen beta-molecular sieve compression molding and 20~40 mesh are sized to, it is spare.Its Acidity is listed in Table 1 below.
The esterification that catalysis acetic acid and sec-butyl alcohol are carried out with the above-mentioned beta-molecular sieves of 3g is evaluated.By acetic acid and sec-butyl alcohol according to
Molar ratio 1:2 are passed through the fixed bed reactors of self assembly, reaction pressure 2.0MPa, weight (hourly) space velocity (WHSV) 0.8h-1, reaction temperature is
110℃.The result shows that：The conversion ratio of acetic acid is 56.34%, and the selectivity of sec-butyl acetate is 88.03%.
Comparative example 2
It is spare by the macropore strong acid cation exchanger resin Amberlyst 15 of Rome＆Hass productions in 90 DEG C of dryings.
The esterification that catalysis acetic acid and sec-butyl alcohol are carried out with the above-mentioned cation exchange resin Amberlyst 15 of 3g is evaluated.
By acetic acid and sec-butyl alcohol according to molar ratio 1:2 are passed through the fixed bed reactors of self assembly, reaction pressure 2.0MPa, weight (hourly) space velocity (WHSV)
For 0.8h-1, reaction temperature is 110 DEG C.The result shows that：The conversion ratio of acetic acid is 41.70%, and the selectivity of sec-butyl acetate is
75.99%.
The result of embodiment and comparative example illustrates, in the esterification of acetic acid and sec-butyl alcohol, metal-modified beta-molecular sieve
The acetic acid that large hole storng-acid cation exchange resin Amberlyst 15 and unmodified Hydrogen beta-molecular sieve have higher converts
Rate and sec-butyl acetate selectivity.Meanwhile metal-modified beta-molecular sieve catalyst of the invention overcomes the work of traditional esterifications catalyst
The shortcomings that property component is easy to run off.The equipment corrosion of traditional handicraft can be also reduced using catalyst provided by the invention, reduces production
Cost.
The Acidity of 1 section Example of table and comparative example catalyst
Note：A is by NH3- temperature programmed desorption characterizes and Origin swarmings fitting gained；B is measured by pyridine IR Characterization and acid
Calculate gained.
Claims (10)
1. a kind of preparation method of modified beta molecular sieve, wherein, the described method includes using beta-molecular sieve as matrix, using metallic element as
Modifying agent, using the solution of metallic element soluble salt, the modified beta molecular sieve is prepared using ion-exchange；The gold
Belong to one or more mixing of the element in Cu, Al, Zn, Fe and Sn；The metallic element is in obtained modified beta molecule
Mass content in sieve is 0.5-4% (being preferably 0.5-3%).
2. preparation method according to claim 1, wherein, the soluble salt of the metallic element is selected from the metallic element
One or more mixing in chloride, nitrate, acetate and phosphate；It is preferred that mole of the metal soluble salt solution
Concentration is 0.1-1.0mol/L；It is preferred that the solution of the metal soluble salt and the ratio of matrix are 5：1mL/g.
3. preparation method according to claim 2, wherein, the solvent in the metal soluble salt solution is selected from water or organic
Solvent；It is preferred that the alcohol that it is 1-4 that the organic solvent, which is carbon number,.
4. preparation method according to claim 1, wherein, the beta-molecular sieve is Hydrogen beta-molecular sieve；Preferably silica alumina ratio
For the Hydrogen beta-molecular sieve of 20-60.
5. according to the preparation method described in Claims 1 to 4 any one, wherein, the described method includes by beta-molecular sieve with it is described
The solution mixing of metallic element soluble salt, the step of stirring 4-10h, (preferably the described method includes by beta-molecular sieve and the metal
The solution mixing of element soluble salt, stirs 4-10h, is then washed with water, is dried to obtain the modified beta molecular sieve).
6. preparation method according to claim 5, wherein, the step of the method further includes roasting, then obtain described
(temperature preferably roasted is 400-600 DEG C to modified beta molecular sieve；It is preferred that the time roasted is 3-10h).
7. modified beta molecular sieve (the preferably described modification beta molecule that the preparation method described in claim 1~6 any one obtains
The specific surface area of sieve is 515~534m2/ g, pore volume are 0.36~0.38cm3/g)。
8. a kind of lactate synthesis method of acetic acid and sec-butyl alcohol, wherein, the synthetic method is included with changing described in claim 7
Property beta-molecular sieve reacted for catalyst.
9. synthetic method according to claim 8, wherein, the reaction is (preferably miniature solid in fixed bed reactors
Fixed bed reactor) in carry out.
10. synthetic method according to claim 8 or claim 9, wherein, the condition of the reaction includes：Reaction temperature is 100-
140 DEG C, reaction pressure is that (preferably the molar ratio of sec-butyl alcohol and acetic acid is (1 to 0.5-2.5MPa:1)-(4:1), weight (hourly) space velocity (WHSV) is
0.5-2h-1)。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711145548.5A CN107899607A (en) | 2017-11-17 | 2017-11-17 | A kind of modified beta molecular sieve and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711145548.5A CN107899607A (en) | 2017-11-17 | 2017-11-17 | A kind of modified beta molecular sieve and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107899607A true CN107899607A (en) | 2018-04-13 |
Family
ID=61846028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711145548.5A Pending CN107899607A (en) | 2017-11-17 | 2017-11-17 | A kind of modified beta molecular sieve and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107899607A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317193A (en) * | 2018-11-12 | 2019-02-12 | 上海第二工业大学 | A kind of application of Fe-SAPO-34 catalyst in methyl stearate synthesis |
| WO2021219064A1 (en) | 2020-04-30 | 2021-11-04 | 中国石油化工股份有限公司 | Modified beta zeolite, catalytic cracking catalyst as well as preparation method therefor and application thereof |
| CN115350727A (en) * | 2022-10-21 | 2022-11-18 | 河北工业大学 | Modified sulfonic acid resin catalyst and preparation method and application thereof |
| CN115722259A (en) * | 2021-08-26 | 2023-03-03 | 中国科学院广州能源研究所 | Synthetic method of space-adjacent bimetallic heteroatom molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945250A (en) * | 2014-03-31 | 2015-09-30 | 中国石油化工股份有限公司 | Method for synthesizing n-butyl acetate |
| CN106622350A (en) * | 2016-12-27 | 2017-05-10 | 广东石油化工学院 | Transition metal modified silicon-aluminum molecular sieve, and method for preparing ester through catalytic esterification of molecular sieve |
-
2017
- 2017-11-17 CN CN201711145548.5A patent/CN107899607A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945250A (en) * | 2014-03-31 | 2015-09-30 | 中国石油化工股份有限公司 | Method for synthesizing n-butyl acetate |
| CN106622350A (en) * | 2016-12-27 | 2017-05-10 | 广东石油化工学院 | Transition metal modified silicon-aluminum molecular sieve, and method for preparing ester through catalytic esterification of molecular sieve |
Non-Patent Citations (3)
| Title |
|---|
| 张静静等: "Sn改性Hβ分子筛催化顺酐酯化", 《工业催化》 * |
| 汤晓君: "Al-β沸石催化合成乙酸辛酯", 《齐齐哈尔大学学报》 * |
| 胡秋凤等: "β沸石分子筛催化合成乙酸正丁酯的反应", 《北京服装学院学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317193A (en) * | 2018-11-12 | 2019-02-12 | 上海第二工业大学 | A kind of application of Fe-SAPO-34 catalyst in methyl stearate synthesis |
| WO2021219064A1 (en) | 2020-04-30 | 2021-11-04 | 中国石油化工股份有限公司 | Modified beta zeolite, catalytic cracking catalyst as well as preparation method therefor and application thereof |
| CN115722259A (en) * | 2021-08-26 | 2023-03-03 | 中国科学院广州能源研究所 | Synthetic method of space-adjacent bimetallic heteroatom molecular sieve |
| CN115722259B (en) * | 2021-08-26 | 2024-02-09 | 中国科学院广州能源研究所 | Synthesis method of space adjacent bimetallic heteroatom molecular sieve |
| CN115350727A (en) * | 2022-10-21 | 2022-11-18 | 河北工业大学 | Modified sulfonic acid resin catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107899607A (en) | A kind of modified beta molecular sieve and its preparation method and application | |
| TW499420B (en) | Catalytic processes for the preparation of acetic esters | |
| TWI612031B (en) | Method and device for co-production of cyclohexanol and alkanol | |
| CN104711007A (en) | Preparation method of aviation kerosene or diesel oil scope liquid alkane | |
| CN110871107A (en) | Catalyst for preparing low-carbon olefin by coupling catalytic cracking of low-carbon alcohol and naphtha as well as preparation method and application of catalyst | |
| CN101455976A (en) | Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof | |
| CN116328825A (en) | Catalyst, preparation method thereof and method for preparing methyl 3-methoxypropionate by using catalyst to catalyze methanol and methyl acetate | |
| CN100402485C (en) | Method for reaction rectification coupling continuous preparation of and series acetate | |
| CN102976892B (en) | Method for preparing ethanol through acetic ester hydrogenation | |
| CN109046445A (en) | A kind of preparation method of H β/MCM-22 composite molecular sieves and the method for preparing tert-butyl phenol | |
| CN108503547A (en) | A method of by transesterification path synthesizing n-butyl acetate | |
| CN104761443A (en) | A method of continuously preparing 3,5,5-trimethyl-3-cyclohexene-1-one | |
| CN100509151C (en) | Application of load type catalyst in synthesizing N phenyl maleimide | |
| CN101703944B (en) | Molecular sieve modified catalyst, preparation method and application thereof to preparation of acrylic ester | |
| CN101439294A (en) | Molecular sieve catalyst for producing ethylene from ethanol dehydration as well as preparation and use | |
| CN110054547A (en) | A method of using integrated catalyst coupling and catalyzing preparing ethanol by oxalate hydrogenation | |
| CN101301624B (en) | Al2O3-HZSM-5 compound solid acid catalyst prepared by chemical precipitation method | |
| CN112774658A (en) | Acid-base bifunctional catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde and preparation method thereof | |
| CN102814193A (en) | Copper-composite molecular sieve catalyst used for synthesis of diethyl carbonate through gas-phase oxidative carbonylation and its preparation method | |
| WO2020155145A1 (en) | Method for preparing ketone organics | |
| CN107915595B (en) | Method for producing polyoxymethylene dimethyl ethers | |
| CN107915601B (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN107915597B (en) | Catalyst for preparing polyformaldehyde dimethyl ether | |
| CN107915602B (en) | Polyoxymethylene dimethyl ether catalyst | |
| CN107915594B (en) | Synthetic method for polyformaldehyde dimethyl ether |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180413 |
|
| RJ01 | Rejection of invention patent application after publication |